TW209231B - - Google Patents
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- TW209231B TW209231B TW080108357A TW80108357A TW209231B TW 209231 B TW209231 B TW 209231B TW 080108357 A TW080108357 A TW 080108357A TW 80108357 A TW80108357 A TW 80108357A TW 209231 B TW209231 B TW 209231B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
- C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
- C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
- C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/378—Thiols containing heterocyclic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Springs (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Description
Λ 6 ^^ 五、發明説明() 本發明偽蘭於一条列之新穎化合物,亦即含聚順式甲基 丁烯二醛亞胺之(聚)硫化物和含聚亞甲基丁二醛亞胺之 (聚)硫化物。本發明亦閼於具有改良物理性質之橡膠組 成物,該橡膠組成物偽於一値或多痼本發明之化合物的存 在下,以硫硫化。本發明亦_於在本發明之待別化合物存 在下所進行之硫化程序,並關於這些化合物在硫化橡嘐時 之使用。最後,本發明亦關於橡膠製品,其包含在本發明 之化合物存在下,以硫硫化的橡膠。 一般而言,聚順式甲基丁烯二舔亞胺和聚亞甲基丁二 篚亞胺為習知物質,可由下列文獻所掲示之方法來製備, 這些文獻包括”雙順式甲基丁烯二諉亞胺與聚雙順式甲基 丁烯二迺亞胺之合成 ” ,G a U n t i , A . V .和 S c ο 1 a , D . A . J 〇 u r n . o f P o 1 y in. S c i .:高分子化學販,v o 1 . 13 , p p 4 5卜4 7 5 , ( 1 9 8 1 )雙亞甲基丁二韹敔和雙亞胺同分異溝 單體之合成 ” ,Galanti, A.V.等人於 Journ. Polyu. Sci. :高分子化學版,V ο 1 . 2 0 , P P . 2 3 3 - 2 3 9 ( 1 9 8 2 );和.Λ 6 ^^ V. Description of the invention () The novel compound of pseudo-blue in the present invention, namely (poly) sulfide containing polycis-methylbutadiene diimide and polymethylene succinaldehyde (Poly) sulfide of imine. The present invention is also directed to rubber compositions having improved physical properties, which are vulcanized by sulfur in the presence of one or more compounds of the present invention. The invention also relates to the vulcanization process carried out in the presence of the compounds to be classified according to the invention, and to the use of these compounds when vulcanizing rubber. Finally, the invention also relates to rubber products, which comprise sulfur-vulcanized rubber in the presence of the compounds of the invention. Generally speaking, polycis-methylbutene diimine and polymethylene succinimide are conventional substances and can be prepared by the methods shown in the following documents, which include "bis-cis-methylbutane "Synthesis of enediimide and polybiscis-methylbutenediimide", Ga U nti, A. V. And S c ο 1 a, D. A. J 〇urn. Of P o 1 y in. S ci.: polymer chemical trader, vo 1.13, pp 4 5 卜 4 7 5, (1 9 8 1) bismethylene butadiene diammonium and bisimine homodimer monomer "Synthesis", Galanti, AV et al. In Journ. Polyu. Sci .: Polymer Chemistry Edition, V ο 1. 2 0, PP. 2 3 3-2 3 9 (1 9 8 2); and.
Hartford, S . L . , 3 u b r a ϊβ a n i a η , S.以及 Parker, J.A·, 經濟部中央標準局貝工消"合作社印rt,,4 (請先閲讀背而之注念事項#填窵本頁) i 0 y r a . foluai. ici.:高分子化學适,;/Qi. 13,P.i3 7 ( 1 9 6 2 ),這些文獻在此處偽作參考用。 除此之外,美國專利第3 , 9 7 4, 1 6 3號揭示了 一些含硫之亞胺。然而在這些亞胺中,硫偽直接鍵結於亞 胺基之氮原子,因此,這些物質與本發明之亞胺有很明顯 的不同。該專利亦掲示了這些含硫之亞胺作為二烯橡過 本紙張尺度逍用中國a家標準(CNS)TM規怙(210x297公龙) 經试部中央櫺準局貝工消费合作杜印¾. 209231 _nj_ 五、發明説明()早硫化之抑制劑的使用。然而,本發明之化合物的持別庚 點並未掲示或建議於該專利案中。 在輪胎和皮帶工業中,較佳之耐機械和耐熱性質是需 要的。長久來己發現橡膠之機槭性質的改良可藉由使用大 量之硫作為交聯劑而增強硫化橡膠的交聯密度。然而,使 用大量硫所産生之缺點為返原之發生並導致最終産物在耐 熱和抗彎曲裂解上有明顯的降低。返原成為持缠性問題之 事實可從”橡嘐微结溝和返原” ,Nordsiek, Dr. K.H., Rubber World, 197(3), pp. 30-38, 1987,和,” Physikalische u n d Cheaische .4 s p e k t a d e r Reversion, ’’ Kautschuk + Guanni-Kunstoffe, 34,9, 1981 中看 出。 為避免上述缺點,有人建議在j it:作用糸统中加入輔 助劑。一種習知頚型之辅助剤為李遨,·,此類硫化条 --- 一-------------“'·一------------〆 統掲示 K 於” VuIeanizaUon Halsiaides,” 應用高 分子期刊,V 0 i. δ , p p· 2231-229 3 (1964 ) 0 美園專利第3, 297, 7 13號案建議使用二硫雙 _ 一 --------* ^ ί ;ΝΪ — ^A S二|女’丨/7t3 k *以‘匕观·化頭:¾而,這値―系 ................. -··' ·..................—· - — ' , —.. - ~------------·" 统並未採用硫作為硫化剤,因此,産生7丨艮_多gl於.胃(暖UI 品中缺乏硫之交聯而導致之缺點υ 曰本專利公告J6 1014〜238掲示了使用馬 來證亞按作為舖助割之硫化条統,且其中φ @ @ 7 1 ^ ft 二苯並嫿唑或四甲秋蘭姆化二硫3然而,此溶液之用途有 (請先閲請背而之注意事項#填寫本頁) 裝_ f -5 - 線· 本紙張尺度逍用中國S家標準(CNS)Ή規格(210X297公;¢) Λ 6 Η 6 經溃部中夾榣爭局员工消t合作杜印製 —— 五、發明説明() 限,因只有具相當短之過早硫化時間的硫化加速劑才可與 雙一馬來醯亞胺一起使用。 歐洲專利申請案0 1 9 1 93 1建議雙-馬來醯亞胺 化合物和次磺醯胺與二硫磷酸之合併使用導致了以硫硫化 橡膠之機械和抗-返原性質之進一步改進。該專利說明書 說明這些橡膠顯示了抗返原,耐熱熟化和抗彎曲裂解的改 進。然而,此条統限於在次磺醯胺加速劑和二硫磷酸加速 劑之存在下所進行之硫化作用,因此,在實際應用上亦受 了限制。 在”以天然橡膠為基質,在含硫化和雙馬來g亞胺之 硫化糸統存在下,绖延長硫化所得硫化産物在結構和性質 上之改變 ’’ C h a v c h i c h, T . A .,等人,1U u c h u k i R e 2 i n a, V 〇 1 4, p p · 2 0 - 3 , 1 9 8 1中掲示了天然浅膠眙面物料(' t r s a d s t q c k s)在對-次苯基雙馬來韹亞胺存在下,於:[ 4 3 t:以硫硫化6 0 0分邊.可得到較佳之椟械性質和較 佳之抗返原性質。 其它顆於使闬雙馬來韹亞胺為舖助_之掾鹽硫化的文 眾S活”以馬栾S亞胺之衍主抅在高溫和輻射作用下硫化 順 — 1,4 —異戊—德橡 _,” κ a u c h u k i β e z i n a , V 〇 1 3,P P · 1 0 _ 1 2,ί 3 7 4 ; ”以馬來韹亞胺之硫代衍生物對未 飽和標驟之進行高溫咖化,” Kauchuk i Rezina, Vol 3, p p ‘ 1 6 - 1 9, 1 9 7 5 ;以及”交聪剤之類型和濃度對雙馬來 鏡亞跋與硫之合併糸统的影蜜.” K d u c h u k i R e 2 i n a , N 0 . 本紙張尺度逍用中a a家«準(CNS) T4規格(210x297公放) (請先閲請背而之注意事項#填窩本頁) 裝· 訂 線· Λ 6 Η 6 五、發明説明() 10, PP. 1 5- 1 9 , 1 9 85 ώ 然而,雖然上逑幾個專利已掲示可藉由添加雙馬來醛 亞胺而降低返原程度,但在實際應用上,雙馬來匿亞胺所 能降低返原之程度仍是不夠的。因此,雖然返原和耐熱之 性質已稍有改善,但仍存在著的問題是仍未有可廣泛應用 之抗原劑,其於硫化程序中可與許多不同之橡膠加速割合 併使用,在對其他橡膠之性質無不利效應時,可令人滿意 地解決返原之問題,同時明顯地改進經硫硫化橡膠之耐熱 性質。 此外,加拿大專利第7 38. 500號掲示了以雙馬 來鏗亞胺和雙順式甲基丁烯鐽亞胺,在無硫之存在下硫化 橡顧。上逑方法為以硫硫化方法的另一種選擇。然而,由 該專利所揭示方法製備之橡璆製品仍是有過氯化物一熟化 嗦®之一般缺點,如低張力以及在其他重要性質之明顯降 低。該專利並未掲示在橡膠之硫一硫化過程中使雙一馬來 薦亞筱或雙一順式甲基丁烯二藏亞胺。 經濟部屮央榣準局3工消伢合作社印製 (請先閲讀背而之注意事項再填寫本頁) 本發明提供了上述問題解決之道,其偽於之硫一 化遇程中使吊新穎含聚!頂式甲基丁盅二S亞按和聚亞甲$ 丁莛亞胺抗返原劑之()硫化物。 本發明之化合物可以通式Α來代表: (Q 1 ) η — D j — { ( S ) ρ — D 2 —〔 ( S ) q — D 3 〕 r - ( Q 2 ) a} z ( A );其中 Di , 和 D3 可 選擇地包含一値或多個S自氮,氣,矽,磷,翊,瓸和亞 本紙ΛΛ度边用中8國家楳準(〇胳)肀4規岱(210父297公*) 209331 A 6 B 6 五、發明説明() 磺醛之雜原子或基園,且為單聚或寡聚二價,三價或四價 基圄,且D2在r不為0時不存在;n, m, z為個別為 選自1, 2或3之整數;p和q痼別為1至8之整數;r 為選自Ο, 1, 2和3之整數;(^1和(^2分別選自式I 、I I : ί -!{Hartford, S. L., 3 ubra ϊβ ania η, S., and Parker, JA ·, Ministry of Economic Affairs, Central Standards Bureau, Bei Gong Xiao " Cooperative Society printed rt ,, 4 (please read the back-to-back notes #filling This page) i 0 yra. Foluai. Ici .: polymer chemistry, / Qi. 13, P.i3 7 (1 9 6 2), these documents are used for reference here. In addition, US Patent No. 3, 9 7 4, 1 6 3 discloses some sulfur-containing imines. However, in these imines, sulfur pseudo-bonds directly to the nitrogen atom of the imine group. Therefore, these substances are significantly different from the imines of the present invention. The patent also shows that these sulfur-containing imines can be used as a standard for diene rubber on paper. The Chinese Standard (CNS) TM regulations (210x297 male dragons) are approved by the Ministry of Test and Inspection, Central Bureau of Industry and Fisheries, and cooperation. . 209231 _nj_ 5. Description of the invention () Use of early vulcanization inhibitors. However, the holding point of the compounds of the present invention is not shown or suggested in the patent case. In the tire and belt industry, better mechanical and heat resistance properties are needed. It has been discovered for a long time that the improvement of the properties of rubber's organic maple can enhance the crosslinking density of vulcanized rubber by using a large amount of sulfur as a crosslinking agent. However, the disadvantage of using large amounts of sulfur is the occurrence of reversion, which leads to a significant reduction in heat resistance and bending cracking resistance of the final product. The fact that return to originality becomes a lingering problem can be found in "Oil Micro-trench and Return to Originality", Nordsiek, Dr. KH, Rubber World, 197 (3), pp. 30-38, 1987, and, "Physikalische und Cheaische .4 spektader Reversion, '' Kautschuk + Guanni-Kunstoffe, 34, 9, 1981. In order to avoid the above shortcomings, it is suggested to add an auxiliary agent to the jit: action system. A conventional auxiliary type is Li Ao, ·, such vulcanized strips --- one ------------- "'· one ------------ 〆 潲 掲 示 K 于" VuIeanizaUon Halsiaides , ”Journal of Applied Polymers, V 0 i. Δ, pp · 2231-229 3 (1964) 0 Meiyuan Patent No. 3, 297, 7 13 recommends the use of disulfide_ 一 -------- * ^ ί; ΝΪ — ^ AS II | Female '丨 / 7t3 k * To' dagger view · Hua Tau: ¾ And, this value-is ........................-· · '· ..................— ·-—', — ..-~ ------------ · " Sulfur is used as the vulcanizing agent, therefore, it has a defect in the stomach (the lack of cross-linking of sulfur in the warm UI products). This patent announcement J6 1014 ~ 238 shows the use of Malayalam As a vulcanization system for auxiliary cutting, and among them φ @ @ 7 1 ^ ft dibenzopyrazole or tetramethylthiuram disulfide 3 However, the use of this solution is (please read the notes beforehand #Fill in this page) 装 _ f -5-Thread · This paper standard uses the Chinese S family standard (CNS) Ή specifications (210X297 g; ¢) Λ 6 Η 6 in the Ministry of Economic Affairs, the employees of the dispute department eliminate cooperation Printed-V. Description of the invention () limit, because only vulcanization accelerators with a relatively short premature vulcanization time can be used with bis-maleimide. European Patent Application 0 1 9 1 93 1 Recommendations The combined use of the bis-maleimide compound, sulfenamide and dithiophosphoric acid has led to further improvements in the mechanical and anti-reversion properties of sulfur-vulcanized rubber. The patent specification states that these rubbers show anti-reversion and heat resistance Improvement of curing and anti-bending cracking. However, this rule is limited to the vulcanization carried out in the presence of sulfenamide accelerator and dithiophosphoric acid accelerator, so it is also limited in practical application. Natural rubber as the matrix, containing vulcanized and bis-maleic imine vulcanized In the presence of the system, the structure and properties of the vulcanization products obtained by the extended vulcanization of the sulfide are changed '' C havchich, T A., et al., 1U uchuki Re 2 ina, V 〇1 4, pp · 2 0-3, 1 9 8 1 shows that the natural light gum surface materials ('trsadstqcks) in the presence of p-phenylene bismaleimide, in: [4 3 t: sulfur sulfide 60 0 points. Can be compared Jiazhi's mechanical properties and better anti-return properties. The other particles are made of bismuth maleimide, which is used as a buoyant. The Wenzhong S live vulcanized by salt sulfide. The derivative of Maluan S imide is cis-1,4-isopentane sulfide under the action of high temperature and radiation. —German Oak _, ”κ auchuki β ezina, V 〇1 3, PP · 1 0 _ 1 2, ί 3 7 4;" Take the thio derivative of maleimide to carry out high-temperature coffee on the unsaturated standard ", Kauchuk i Rezina, Vol 3, pp '1 6-1 9, 1 9 7 5; and" The type and concentration of Jiao Congjiao's shadow honey for the merger of Shuangmalai Jingyaba and Sulfur. " K duchuki R e 2 ina, N 0. This paper standard is easy to use aa home «standard (CNS) T4 specifications (210x297 public release) (please read the back to the precautions #fill nest this page) installation · binding · Λ 6 Η 6 5. Description of the invention () 10, PP. 1 5- 1 9, 1 9 85 However, although several patents have been published, it can be shown that the degree of reversion can be reduced by adding bismaleimide However, in practical applications, bismaleimide can still reduce the degree of reversion. Therefore, although the properties of reversion and heat resistance have been slightly improved, there is still the problem that there is still no widely used antigen agent, which can be combined with many different rubber accelerated cutting in the vulcanization process. When the properties of rubber have no adverse effects, the problem of reversion can be satisfactorily resolved, and the heat resistance properties of sulfur-vulcanized rubber are significantly improved. In addition, Canadian Patent No. 7 38.500 shows that bismaleimide and biscis-methylbutene-imide are used to vulcanize rubber in the absence of sulfur. The upper method is another option for sulfur vulcanization. However, the rubber gadgets prepared by the method disclosed in this patent still suffer from the general disadvantages of perchloride-cured®, such as low tension and significant reduction in other important properties. This patent does not show the use of bis-maleimide or bis-cis-methylbutene diimide during the sulfur-vulcanization of rubber. Printed by Cooperative Society 3 of the Ministry of Economic Affairs and the Ministry of Economic Affairs (please read the precautions before filling out this page) The present invention provides a solution to the above problem, which is caused by the pseudo-sulfurization process. Novel and Poly! Top-type methyl butadiene disulfide and polymethylene $ butylidene imide anti-reversion agent () sulfide. The compound of the present invention can be represented by the general formula A: (Q 1) η — D j — {(S) ρ — D 2 — [(S) q — D 3] r-(Q 2) a} z (A) ; Where Di, and D3 can optionally contain one or more S from nitrogen, gas, silicon, phosphorous, yi, urethane, and ababen paper, with 8 countries in the national standard (〇) 悀 4 regulations Dai (210 Father 297 Gong *) 209331 A 6 B 6 V. Description of invention () Sulfuraldehyde heteroatom or base garden, and it is a mono- or oligomeric divalent, trivalent or tetravalent base, and D2 is not 0 Does not exist; n, m, z are individually integers selected from 1, 2 or 3; p and q are respectively integers from 1 to 8; r is an integer selected from Ο, 1, 2 and 3; (^ 1 and (^ 2 are selected from formula I and II respectively: ί-! {
Ri r -C-C-fI -c-r3 (!) Λ \ r2 (Π) (請先閲讀背而之注意事項#填寫本頁) -c-r3 其中R ,C 3 及C 7 併而形 更 應産物 (A ) 經濟部中央檫準局貝工消许合作社印製 (C ) 此 行的硫 化反應 ί , R 2 —C ί 3 —C 30 院 成一環; 持別地, 之硫_硫 至少一種 0 . 1至 ,可提供 0 . 1至 外,本發 化方法, 中的使用 和R 3画 環垸基, 芳基,以 B和Β ί 本發明在 化掾膠组 ;妖甙会 ,·’、 ,》·、 1—1 2 5伝重 0 . 1至 5 . 0份 明關於在 以及式A 。再者, 5 丨j 52 運曰 m , i — u i f m ^ C。一 C i 3芳基,C 30芳烷基 及R 2和R 3在R i為氫時可合 分別為選自氧和硫之雜原子.: 第二方面淫關於包活下列硫化反 成物: 成像蹼 β ^ K? 2 5份 重量之 式Α之 之抗返 本發明 -7 - ,其重量為1 0 0 w ; t:n , ;Ti ΛΪ1 ίΐί^ 十有窖 j :~t ,· ^ ~ * . -* v .ygr. -— 麯·v ··.*_<* .- i_— 當量重之硫;以及 式A的輔肋劑。 抗返原輔肋劑之存在下進 原铺肋劑在橡嘐之硫一硫 亦包括了包含有至少一些 良紙張尺度遑用中a S家楳準(CNS) 規格(210X297公龙) •tr Λ 6 B 6 五、發明説明() 橡膠在式A之上述抗返原輔肋劑之存在下經硫硫化之橡膠 製品。 本發明之輔助劑提供了優良之抗返原效應,以及對其 他性質不産生明顯之逆反應下,改善了許多橡膠性質,這 是與採用其他輔助劑之類似硫一硫化条統來作比較。 在不以任何恃別理論限制之下,本發明之抗返原輔肋 劑解決了硫-硫化橡膠返原之長久存在的問題,此乃因本 發明之抗返原割在硫-硫化狀況下是相當不活潑的,因此 ! ,在最適熟化時,仍有相當量之輔肋劑存留於橡膠組成物 中,使得铺肋劑在最適熟化後和當返原之問題發生之過度 熟化時,可與經硫一硫化之豫穋反應形成額外的交聯。對 於最適熟化之定義請参見,W . Hof n»ann, ”橡膠技術學手 冊”。 本發明之式A化合物為新穎化合物,且可由”雙頭式 甲基丁烯二證亞按和聚雙順式甲基丁烯二薦亞胺之合成” Galanti, A.V.和Seola, D.A.於高分子科學期刊:高分子 化學版,V ο 1 1 '3, p p 4 5 1 - 4 7 5 , ( 1 9 3 1);和”雙亞甲基丁 經濟部中夬櫺準局只工消佾合作杜印製 (請先閲讀背而之注意事項洱塡寫本頁) 二ϋ盏,叟亞胺單Μ異S之合或” ,G a i ^ i i , A . V .;人 ,於高分子科學期刊:高分子化學版,V ο I 20 , pp . 233-239(1932)和 Hartford, S . L . , Subraaianian, S.和 Parker, J . A .,高分子科學期刊:高分子化學版,V 〇 1 . 16, P.1 3 7, 1 9 3 2中所掲示之方法來製備,以上所述之文獻 傜用作參考:,當然,這些合成法須Μ由還擇包括t聚)硫 k紙張尺度遑用中S Η家標準(CNS) T4規格(210x297公龙) 209^1 五、發明説明() Λ 6 It 6 經濟部中央櫺準局只工消评合作社印製 硫 化 物 之 反 應 物 來 作 小 幅 修 正 » 以 獲 得 本 發 明 之 包 含 ( 聚 ) 硫 化 物 的 亞 胺 〇 本 發 明 最 佳 之 亞 胺 化 合 物 * 以 式 A 表 示 者 > 包 括 (並 非 限 制 於 此 ) , 雙 順 式 甲 基 丁 烯 二 醒 亞 胺 • 其 Q X 和 Q Ζ 為 式 I » R 1 = R Z = R 3 = Η » η = 1 且 B = B 1 = 氯 m 亞 甲 基 丁 二 驗 亞 胺 t 其 中 Q 1 和 Q 2 為 式 I I » R 1 = R Z = R 3 = Η » η = 1 且 Β = Β I = 氯 > 順 式 甲 基 丁 烯 二 韹 亞 胺 和 亞 甲 基 丁 二 SI 亞 胺 之 混 合 t 其 中 Q 1 為 式 I , Q 為 式 I I * R 1 = R 〇 = R 3 = Η > η = 1 且 B = B 1 氯 以 及 上 述 化 A 物 之 混 合 物 更 持 別 地 * 式 A 甲 所 提 到 之 D 1 » D 〇 和 τ~-. 3 可 為 i ; >.-.1 举 聚 二 價 > 三 價 或 四 價 直 m 或 支 m 基 選 白 C 1 — C 1 ί fee 基 1 C — C 1 3 烯 基 % C — C 1 3 炔 荃 > C 3 一 C 1 環 院 基 » C 2 — C 30 聚 環 基 * C 〇 — c 1 Ξ 芳 基 » C C — C 3 聚 芳 基 , C 7 — 30 号 λ兀 基 ♦ C 7 — 30 芳 基 * 一 屆 --八 多 ί@ 這 基 之 寡 聚 物 t 且 這 基 可 m 擇 性 地 a 括 iH pV -;Ai 多 U£J 氧 * -*Τ=· t 矽 t * 題 * 硫 氯 和 » 所 有 、 Is itb 基 -ΓΓΓ 'M11 可 -MB s 1XSB i_ rib Ξ 'ΠΠ it^J 選 自 r m * 矽 • 二 氯 :L· IL. T U. '·· .. 亞 rt-L· ^£: t oai 胺 基 t 亞 胺 基 » 厲 氛 » 二 IS 氛 t ^ΓΤ TTV, m 胺 基 f 氯 化 偶 氛 基 * 院 氯 基 t 羥 基 » 5典 1 氣 1 溴 * 氛 t m 基 t 羧 =±fci * 酯 t s 〇 2 » s 0 3 , 胺 m 基 » S i 0 3 * 硝 基 > 亞 t=ea 胺 基 t *Μ 代 锻 基 r η 基 ) 和 環 氯 基 之 取 代 s 於 一 魅 -ίΑ» 画 原 子 之 基 取 代 (請先閲讀背而之注意事項洱堝寫本頁) 209讲 Λ 6 Η 6 經濟部屮央榀準局A工消伢合作杜印¾ 五、發明説明() 本發明中一些有用之亞醯胺化合物較持別之例子如下 (並非限制於此)。雙(2-順式甲基丁烯二醛亞胺乙基 )硫化物,雙(2 —順式甲基丁烯二醯亞胺乙基)二硫化 物,雙(2—順式甲基丁烯二舔亞胺乙基)聚硫化物,雙 (3_順式甲基丁烯二醯亞胺丙基)二硫化物,雙(4 — 順式甲基丁烯二醯亞胺一 2 —甲基丁基)二硫化物,雙( 2 —順式甲基丁烯二鏟亞胺環已基)二硫化物,2 —順式 甲基丁烯二葭亞胺乙基一 3 — .頃式甲基丁烯二韹亞胺丙基 硫化物, 1, 2 -雙(2 —順式甲基丁烯二S亞胺苯基硫代)一乙 .院, 1 , 2 —雙(2 —順式甲基丁烯二醯亞胺一13 —氛苯基硫 代i 一乙综, 1. 4_雙(2 —順式甲基丁烯二ϋ亞胺苯基硫代)一丁 烯-2 , 1, 3_雙(2 —頒式甲基丁烯二羞亞胺苯基硫代)一丙 - 2 , a > a 1 — 3 ; 一!頃瓦9金j λ#二逛亞胺笨基硫代;— m —二甲苯, 2 —順式甲基丁插二ϋ亞胺乙基一 2 -順式甲基丁烯二酸 亞胺苯基硫化物, 雙(4 一嚼式甲基丁烯二藍亞按苯基)二硫化物, 雙ί 4 -順式甲基丁烯二證亞按一3 —氛苯基)二硫化物 _ 1 Λ _ 本紙张尺度边用中國Η家榣準(CNS) Τ4規格(210x29/公龙) (請先閲讀背而之注意事項#填寫本頁) 裝. #. 線- ο _ 五、發明説明() 經濟部中央榡準局CX工消伢合作社印製 硫 } 1 ] 物硫 胺胺混亞 化乙 I 二 代 I 基 化二 亞亞為以 硫苯腫 ) 硫 } 笨 硫 }iiil可圃 之 ,烯 , ,基 基 代 基 二基 二 二亦基 膠_丙 物 -物苯 乙 硫 甲 丨苯 T 烯物胺 橡橡, 化物化基 胺 基 二 基胺 基 丁合亞 成然膠 硫化硫氣 亞 乙 I 乙亞 甲基化醯 合天橡 二 硫四甲 醛 胺 6 基韹 亞甲之二 和} 烯 )))_ 二 亞 , 氧二 一式述烯 然此二 基基基4烯S2 乙烯 四 順上丁 天於戊 苯苯苯一 丁 二 I 胺丁 和之 。基 有制異 胺胺胺胺 基 烯 胺 亞基 I 有代甲 所限, 亞亞亞亞 甲 ,丁 亞S甲 叁所取式 於非膠 醛醛醯醯 式塩基S2二式 -惟所順。用並橡 二 二二二 順酸甲 二 烯順 I ,按分代使 f 烯 烯烯烯烯 I 氡式 :g 丁二 雙同亞部取可括二 丁 丁丁丁 2 聚順 ,丁 基 I 之相3!將圑物包丁 基基基基 ί 三一唑基 甲 5 明物二 要基合子, 甲甲甲甲 叁I I 2 二甲 式, 發合 丁只胺化例 _ 式式式式 I 5丨噻式 順 3 本化基,亞之之橡 順順順順 6 -雙 I 順 ,I I、 ,述甲肢韹明嘐烯 - - - _ , 3 一 4 I 物,雙 外上亞11二 發橡二 2 2 2 2 ,4 ,5 , 4 化 2 及 。此 與以 亞丁 本些丁 ,ί < 物 ,1 , 3 ί 硫丨以物 可ίι之基 這 | 雙雙雙雙化 2 I 2 ,雙 二雙 ,化 亦基合甲 。烯 (請先閲讀背而之注意事項再填寫本頁) 本紙張尺度逍用中a Η家標準(CMS)<tM規格(210x297公龙) 2〇923iRi r -CC-fI -c-r3 (!) Λ \ r2 (Π) (please read the notes before entering # fill in this page) -c-r3 where R, C 3 and C 7 are more suitable Product (A) Printed by the Cooperative Society of the Central Sassafras Bureau of the Ministry of Economic Affairs (C) The vulcanization reaction of this trip ί, R 2 —C ί 3 —C 30 The courtyard is a ring; otherwise, at least one of sulfur and sulfur 0. 1 to, can provide 0.1 to the outside, the use of this method, and R 3 to draw cycloalkyl, aryl, to B and Β ί The present invention in the chemical gel group; demon glycoside, ',, "·, 1-1 2 5 伝 weight 0.1 to 5.0 parts clearly about the formula and A. Moreover, 5 丨 j 52 Yun said m, i — u i f m ^ C. A C i 3 aryl group, C 30 aralkyl group and R 2 and R 3 when R i is hydrogen may be a heteroatom selected from oxygen and sulfur, respectively. : Imaging webs β ^ K? 2 5 parts by weight of the anti-return formula of the present invention -7-, its weight is 100 0 w; t: n,; Ti ΛΪ1 ίllί ^ ten Youjiao j: ~ t, · ^ ~ *.-* v .ygr. -— Qu · v ··. * _ < * .- i_— equivalent heavy sulfur; and auxiliary rib of formula A. The presence of anti-returning auxiliary rib agent in the presence of the original rib agent. The sulfur-sulfur in the oak also includes at least some good paper size. The use of a 戳 楳 quasi (CNS) specifications (210X297 male dragon) • tr Λ 6 B 6 V. Description of the invention () Rubber products with sulfur vulcanized in the presence of the above-mentioned anti-return auxiliary rib agent of formula A. The adjuvant of the present invention provides an excellent anti-return effect and improves many rubber properties without significant reverse reaction to other properties, which is compared with similar sulfur-vulcanization systems using other adjuvants. Without being bound by any different theory, the anti-returning auxiliary rib agent of the present invention solves the long-standing problem of reversion of sulfur-vulcanized rubber. This is because the anti-returning of the present invention is under sulfur-vulcanization conditions. Quite inactive, therefore! At the time of optimal curing, there are still a considerable amount of auxiliary ribs remaining in the rubber composition, so that after optimal curing and when the over-curing occurs when the problem of reversion occurs, it can be compared with The sulfur-sulfurized Yu-Yu reaction forms additional cross-links. For the definition of optimal maturation, see W. Hof n »ann," Handbook of Rubber Technology ". The compound of formula A of the present invention is a novel compound, and can be synthesized from "bi-headed methylbutene divinylic acid and polybiscis-methylbutene diimide" Galanti, AV and Seola, DA in polymers Scientific Journal: Polymer Chemistry Edition, V ο 1 1 '3, pp 4 5 1-4 7 5, (1 9 3 1); and "The Ministry of Economic Affairs of the Ministry of Economic Affairs of the Ministry of Economics of Bis-Methylene Butyl" Made by Du Yin (please read the notes on the back to write this page first) Er zhan, the combination of monoimine and isoimide ", Gai ^ ii, A. V .; People, in Polymer Science Journal: Polymer Chemistry Edition, V ο I 20, pp. 233-239 (1932) and Hartford, S. L., Subraaianian, S. and Parker, J. A., Journal of Polymer Science: Polymer Chemistry Edition, V 〇1. 16, P.1 3 7, 1 9 3 2 prepared by the method shown above, the above-mentioned literature is used as a reference: Of course, these synthesis methods must also include t) sulfur k The paper standard is used in the Chinese Standard (CNS) T4 specification (210x297 male dragons) 209 ^ 1 V. Description of the invention () Λ 6 It 6 The Central Bureau of Economic Development of the Ministry of Economic Affairs only evaluates the reaction of sulfide printing by cooperativesTo make minor corrections »To obtain the imine containing (poly) sulfide of the present invention. The best imine compound of the present invention * represented by Formula A> Including (but not limited to), bis-cis-methylbutane Dioximide • Its QX and Q Z are of the formula I »R 1 = RZ = R 3 = Η» η = 1 and B = B 1 = chloromethylene methylene succinimide t where Q 1 and Q 2 is the formula II »R 1 = RZ = R 3 = Η» η = 1 and Β = Β I = chlorine> cis-methylbutene diammonium imide and methylene butadiene diimide mixed t Q 1 is formula I, Q is formula II * R 1 = R 〇 = R 3 = Η > η = 1 and B = B 1 The mixture of chlorine and the above compound A is more specifically * Formula A mentioned The D 1 »D 〇 and τ ~-. 3 can be i; > .-. 1 in the case of divalent polymerization > trivalent or tetravalent straight m or branch m base selection white C 1 — C 1 ί fee base 1 C — C 1 3 alkenyl% C — C 1 3 acetylene > C 3-C 1 cyclic courtyard » C 2 — C 30 polycyclic group * C 〇— c 1 Ξ aryl group »CC — C 3 polyaryl group, C 7 — 30 λ sulfide group C 7 — 30 aryl group * One session-- 八 多 ί @ This group of oligomers t and this group can optionally include iH pV-; Ai more U £ J oxygen *-* Τ = · t silicon t * question * sulfur chloride and »all, Is itb group-ΓΓΓ 'M11 Ke-MB s 1XSB i_ rib Ξ' ΠΠ it ^ J is selected from rm * silicon • dichloro: L · IL. T U. '·· .. sub rt-L · ^ £ : t oai amino group t sub Amino group »Li atmosphere» Di IS atmosphere t ^ ΓΤ TTV, m Amino group f Chlorinated azo group * Yuan chloro group t Hydroxy group »5 Code 1 Gas 1 Bromine * Atmosphere tm group t Carboxylic acid = ± fci * Ester ts 〇2 »S 0 3, amine m group» S i 0 3 * nitro > subt = ea amine group t * Μ substituted forging group r η group) and cyclochloro group substitution s Base substitution (please read the notes on the back of Erguo first to write this page) 209 Lecture Λ 6 Η 6 Ministry of Economic Affairs, Central Bureau of Industry and Commerce A Industrial Consumer Cooperation Du Du ¾ V. Description of the invention () Some useful in this invention Amide compound Examples of more differences are as follows (not limited to this). Bis (2-cis-methylbutenedialdehydeimineethyl) sulfide, bis (2-cis-methylbutenediimideethyl) disulfide, bis (2-cis-methylbutyrate Ethylenediimide ethyl) polysulfide, bis (3_cis-methylbutenediimidepropyl) disulfide, bis (4-cis-methylbutenediimide-2-) Methyl butyl) disulfide, bis (2-cis-methylbutene diethylenimine cyclohexyl) disulfide, 2-cis-methylbutene dioximine ethyl-3-. Formula methylbutene diimide propyl sulfide, 1, 2-bis (2-cis-methylbutene di S imine phenyl thio) Yi B. Institute, 1, 2, 2-bis (2- Cis-Methylbutene diimide-13-ambient phenylthio I-ethyl synthesis, 1. 4_bis (2-cis-methylbutene diimide phenylthio) -butene- 2, 1, 3_Bis (2—Methylbutene Diimide Phenylthio) -Propane-2, a > a 1—3; One! Arewa 9 金 j λ # 二 走 亚Aminbenzylthio; — m — xylene, 2 — cis methyl butadiene diimide ethyl 2- 2-cis methyl butenedioic acid imine phenyl sulfide Bis (4 mono-methylbutene dicyanidene phenylene) disulfide, bis 4 -cis-methylbutene diazidene according to a 3-atmosphere phenyl) disulfide _ 1 Λ _ this paper The Zhang scale uses the Chinese 漣 榣 准 (CNS) Τ4 specification (210x29 / male) (please read the backing notes first #fill this page) to install. #. 线-ο _ V. Description of invention () Ministry of Economic Affairs Printed by the Central Bureau of Precinct CX Industrial Consumer Cooperatives of sulphur} 1] thiamine amine mixed with ethylene I second generation I thiolated with sulfydene sulfide) sulphur} stupid sulphur , Base-based base two base two base rubber _ propylene-material phenethyl sulfide methyl benzene T enenamine rubber rubber, chemical compound base amino two base aminobutadiene rubber gum sulfur sulfur ethylene I Ethylene methylated acetal dithiotetraformaldehyde amine 6-based methylene bis and} ene))) _ _ di-, oxy-di-formation of this diyl-based 4 ene S2 ethylene tetracis Shang Dingtian and fenbutibenzene-butadiene-I-butamol and it. It is based on the production of isoamine amine, amino enamine subunit I. It is limited by the substitution of methyl, sub-methylene, methylene, butylene S, and trimethyl. . Use acryldidioic acid methadiene cis I, according to the generation of f enene ene ene I radon formula: g succinic diisocyanate can be taken to include dibutyl butyl butyl 2 polycis, butyl I phase 3! The encapsulated product contains butylyl group ί triazolyl methyl 5 Mingwu dibasic group zygote, methyl methyl methyl three II 2 dimethyl, dimethyl butamine only _ 式 式 式 式 I 5 丨Thio-cis 3 base group, sub-rubber shun-shun-shun 6-double I-shun, II,, described in the arsenal of sperm---_, 3-4 I, double outer upper Asian 11 second round Oak 2 2 2 2 2, 4, 5, 4 and 2 This is the same as that of Aden, some things, 1, 3, and thiol, which can be based on things. This | double double double double 2 I 2, double double double, double base double. Ene (Please read the precautions before filling in this page) This paper is used in a standard Η home standard (CMS) < tM specifications (210x297 male dragon) 2〇923i
經试部中央榀準局C3:工消费合作杜印M 五、發明説明() 丁二烯橡膠,氣丁二烯橡膠,異戊二烯一異丁烯橡膠,漠 化之異戊二烯-異丁烯橡膠,氯化之異戊二烯-異丁烯橡 膠,乙烯一丙烯一二烯叁聚物,以及兩種或多種這些橡膠 之組合,一種或多種這些橡瘳與其他橡膠和/或熱塑性橡 膠之組合。 可用於本發明之硫的例子包括不同類型之硫,如粉末 硫,硫沈澱和不可溶硫。此外,硫給予體亦可使用以代替 硫,或除硫之外再使用,以期於硫化過程中提供所需程度 之硫。此類硫給予體之洌子包括(並非限制於此)四甲秋 蘭姆化二硫,四乙秋蘭姆化二硫,四丁秋蘭姆化二硫,二 戊甲烯秋蘭姆化六硫,二戊申烯秋蘭姆化四硫,二硫二嗎 啉以及其混合物:· 在本文中,硫之参者锪包括硫给予_和硫與硫绐予疆 之混合物此外,在硫化過程中所使用硫之参考量,當鹽 甩於硫绘予證時,指足夠提洪所指定之相等量硫的硫给予 SH .虽::· 硫與橡膠化合之量,以10 ◦份滓穋為基準,通常為 ύ . 1至£5仿重,且?鉸!^芎0· 2至Siz/S_ 硫绘于藤 與橡嘐化合之量為足夠提ί共t目等量,如同使用硫本身之量 式A之抗返原割與橡瘳化合之量,以1 0 0份橡勝計 ,為0. 1至5份重,且較佳為0. 2至3. 0伤重。所 使用之成份可先混合,或者同時加入或分離,並且他們可 (請先閲讀背而之注意事項外構寫本頁) 裝. 訂 線· 本紙張尺度边用中a困家標準(CMS)TM規格(210x297公tf) Λ 6 η 6 五、發明説明() 與其他橡膠化合成份一同加入。 在大多數情況下,亦可於橡膠化合物中包含硫化加速 劑,可使用傳統,習知之硫化加速劑。較佳之硫化加速劑 包括魏基苯並噻唑,2. 2’ 一巯基並噻唑二硫化物,次 磺醛胺加速劑,包括N-環己基一2-苯並睡唑次磺醯胺 ,N —第三一丁基—2 —苯並噻唑次磺醛胺,以及2 — ( 經濟部屮央櫺準局员工消伢合作杜印驭 嗎啉硫代) 硫代胺基甲 證次磺醯胺 所使用 成物計.為 ,以1〇0 其他傳 強劑如颉黒 镇充劑之混 工油,_拈 可塑劑,加 馥和氯化鋅 發明结合之 ,”橡膠技 苯並噻 酸酯, ,黃酸 之硫化 從0 · 份橡膠 统橡嘐 ,矽石 合物可 劑,蠟 工铺肋 .可以 更完整 術學手 217-353, Hanser 再者,過早硫 唑;硫磷酸衍生物加速劑, 二苯基M,二原甲苯胍.二 塩,三連氪加速劑以及其混 加速劑之量,以1 0 〇份重 1至8份重。較佳地,硫化 重量計,為0. 3至4. 0 添加割亦可以一般用量來使 ,黏土,白堊或其他礦物填 包含於隐P組成物中。其他 ,抗氧化割,抗臭氯割,顔 割,油音,化合割以及活化 傳統,習知之量S活在内:. 的橡嘐添加割的紋述參見, 冊,第4章.橡嘐化物和添 Publishers, Munich 1 9 8 9 〇 化延遲劑如郯苯二甲酐,苯 秋蘭姆,二 硫代胺基甲 合物。 量之橡_組 加速劑之量 用。例如增 充割,以及 添加劑如加 料,樹脂, 割,如硬脂 對於可與本 M . Hofmann 加割” ,PP 均四酸酐( pyromellitic anhydride),笨六甲酸三 Sf. 4 —甲基鄹 私紙張又度逍用中a 8家標準(CNS) T4規怙(2〗0x297公;¢) (請先閲讀背而之注意事項再塡寫本頁) _116_ Λ 6 五、發明説明() 苯二甲酐,苯偏三酐(trinellitic anhydride) , 4-氣 鄰苯二甲酐,N_環己基一硫代鄰苯二甲醯亞胺( N-cyclohexyl-thiophthalinide),水楊酸,苯甲酸,順 丁烯二酐和N —亞硝基二苯胺亦可以傳統,習知之量包括 於橡膠組成物中。最後,s t e e 1 c 〇 r d a d h e s i ο n在持定之應 用中,亦可包括鋼條促進割如鈷塩和二硫代硫酸塩,以傳 統,習知之量存在。 本發明亦關於一種硫化方法,包括於0 . 1至2 5份 重之硫或每100份重橡膠含一硫給予體之存在下,硫化 至少一種天然或合橡瘳之步缀,其持歡在於上述方法偽於 有效量之式A铺肋割的存在下進行。 上述方法鉻Si 1 1 0 — 220f之溫度下,绖至 多2 4小時之時間來完成.更待別地,該方法1 2 0 — 1 9 0 :C之溫度下,於0 . 1至5 . 0份重之抗返原辅肋割 之存在下,經8小時之時間來完成:,更佳地為使用0. 2 至3 . 0份重之抗返原铺助割:所有上述II於橡瞟組成物 之添加割亦可於本發明之硫化過程中存在,: 經濟部中央標準;员工消伢合作社印製 (請先閲讀背而之注意事項#填寫木頁) 在一杖s硫丨b万;·去方;5之具鼸實避阈中,it it ^ 54' 1 2 0 _ 1 9 0 t:之溫度下,在至少一種硫化加速劃,以1 〇0份橡瘳計,為0 . 1至8 . 0份重之存在下,經多至 8小時之時間來完或。, 本發明亦包括在標缪之硫一硫化過程中使用式A之抗 返原铺肋劑:, % Λ 6 η 6 五、發明説明() 最後,本發明亦包括物品之製備.如輪胎,其包含在 式A之抗返原輔助劑在下硫化之硫-硫化橡膠。 本發明進一步以下列實施例來說明,但並非意圖去侷 限發明範圍。本發明之範圍可由其後之申請專利範圍來決 定。H-NMR光譜傜由使用TMS為内部標準之Brukei: W P 2 0 0 S Y 記錄。 實施例1 萑隹 2 _順式甲基丁烯二匿亞胺乙基)二硫化物之合成 在 28. 1 5 克脱胺二亞® (cystamine ) 2 H C 1 和2 2克醋誌納於1 5 Ο毫升二甲苯之Μ拌漿液中。加入 2 8 . 1 0克之擰康酐 icitraconic anhydride)。加熱 並迴流混合物,並將所形成之水積於D e a η - S t a r k裝置中 於不再形成水時,冷卻漿液,並遇濂以去除塩類5於真空 下蒸餾澄清溶液以去除二甲笨:.所得到之黏稠暗色油(4 1. 5克)在靜置下缓®地结晶。在從乙醇中再结晶後, 可得到熔點為 5 . 2 之乳色産物。由Η (請先閲讀背而之注意事項再填寫本頁) 經濟部屮央標準局员工消"合作杜印製 N M R數據可辨別岀該産 亞胺乙基)二硫化拗:C3 of the Ministry of Economic Affairs of the Ministry of Testing: Industrial-Consumer Cooperation Duin M V. Description of the invention () Butadiene rubber, gas butadiene rubber, isoprene-isobutylene rubber, desertified isoprene-isobutylene rubber , Chlorinated isoprene-isobutylene rubber, ethylene-propylene-diene terpolymer, and a combination of two or more of these rubbers, one or more of these rubber galls and other rubber and / or thermoplastic rubber combination. Examples of sulfur that can be used in the present invention include different types of sulfur, such as powder sulfur, sulfur precipitation, and insoluble sulfur. In addition, sulfur donors can also be used instead of sulfur, or in addition to sulfur, to provide the required level of sulfur during the vulcanization process. Such sulfur donors include (but are not limited to) tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, and dipentyl thiuram disulfide. , Dipentene, thiuram, tetrasulfide, dithiodimorpholine and mixtures thereof: · In this article, the ginseng sulfide of sulfur includes sulfur-giving _ and a mixture of sulfur and sulfur-sulfur-jiang The reference amount of sulphur used, when the salt is thrown in the sulphur painting for certification, refers to the sulphur that is sufficient to lift the equivalent amount of sulphur specified by the flood to give SH. Although :: · The amount of sulphur combined with rubber, with 10 ◦ parts as The benchmark is usually ύ. 1 to £ 5 imitation, and? Hinge! ^ Xiong 0 · 2 to Siz / S_ The amount of sulfur painted on the rattan and oak is enough to increase the total amount of the t-mesh, as is the amount of the combination of anti-returning and oak gall combined with the amount of sulfur itself. 1 至 5 份 重。 It is 0.1 to 5 parts by weight, and preferably 0.2 to 3.0. Injury weight. The ingredients used can be mixed first, or added or separated at the same time, and they can (please read the precautions and write this page first) to install. Threading · The paper size is used in the middle of the trapped home standard (CMS) TM specification (210x297 public tf) Λ 6 η 6 V. Description of invention () Add it together with other rubber chemical compounds. In most cases, a vulcanization accelerator may also be included in the rubber compound. Conventional, conventional vulcanization accelerators can be used. Preferred vulcanization accelerators include Weiylbenzothiazole, 2. 2′-mercaptothiazole disulfide, sulfenalamide accelerators, including N-cyclohexyl-2-benzobenzoxazole sulfenamide, N — The third one butyl-2-benzothiazole sulfenal amine, and 2— (employee cooperation of the Ministry of Economic Affairs, Pyongyang Bureau, Du Yinyu, morpholine thio) sulfamidomethine sulfenamide It is calculated by using the compound. It is based on the combination of other strength-transmitting agents, such as Yanqi Town Filling Agent, plasticizer, plasticizer, zinc chloride and zinc chloride. "Rubber technology benzothioate, , Vulcanization of yellow acid from 0 · rubber rubber, silica compound agent, waxwork ribs. Can be more complete technical hand 217-353, Hanser Moreover, premature thiazole; sulfuric acid phosphoric acid derivatives accelerated The amount of the agent, diphenyl M, diorthotoluidine. Di 塩, triple krypton accelerator and its mixed accelerator, is 1 to 8 parts by weight of 100 parts. Preferably, it is 0 by weight of vulcanization. . 3 to 4.0 can also be added in a general amount to make cut, clay, chalk or other minerals contained in the hidden P composition. Other, anti-oxidation cut, anti-odor chlorine cut Yan cut, oil sound, compound cut and activation of tradition, the amount of knowledge S live in: the description of the addition of the cut of the oak, please refer to the book, Chapter 4, Oak Compounds and Tim Publishers, Munich 1 9 8 9 〇 Chemical retarders such as phthalic anhydride, benthiuram, and dithioamine formaldehyde. The amount of the rubber_group accelerator is used. For example, to increase the cutting, and additives such as additives, resins, cutting, such as For stearin, it can be added with this M. Hofmann ”, PP pyromellitic anhydride, hexacarboxylic acid tri Sf. 4—methyl sulfonate, and it can be used in a 8 standard (CNS) T4 regulations. (2〗 0x297 Gong; ¢) (Please read the precautions before writing this page) _116_ Λ 6 5. Description of the invention () Phthalic anhydride, trinellitic anhydride, 4-gasoline Phthalic anhydride, N-cyclohexyl-thiophthalimide (N-cyclohexyl-thiophthalinide), salicylic acid, benzoic acid, maleic dianhydride and N-nitrosodiphenylamine can also be traditional The conventional amount is included in the rubber composition. Finally, s t e e 1 c 〇 r d a d h e s i ο n in the application of holding, can also include the steel bar to promote cutting such as cobalt and dithiosulfate, in traditional, conventional amounts. The present invention also relates to a vulcanization method, which includes vulcanizing at least one natural or synthetic rubber step in the presence of 0.1 to 25 parts by weight of sulfur or one sulfur donor per 100 parts by weight of rubber. This is because the above method is carried out in the presence of an effective amount of formula A rib cutting. The above method is completed at a temperature of chromium Si 1 1 0-220f, at most 24 hours. More to wait, the method 1 2 0-1 9 0: C temperature, at 0.1 to 5. In the presence of 0 parts of the anti-back to the original auxiliary rib cutting, it takes 8 hours to complete :, better to use 0.2 to 3.0. 0 parts of the anti-back to the original shop to help cut: all the above II is in oak Addition and cutting of the composition can also be present in the vulcanization process of the present invention: Central Standard of the Ministry of Economic Affairs; Printed by the Employee Consumer Cooperative (please read the back and notes #fill in the wooden page) in a stick of sulfur 丨 b Million; · go to the side; 5 with a tang to avoid the threshold, it it ^ 54 '1 2 0 _ 1 9 0 t: at a temperature, at least one vulcanization accelerated stroke, calculated as 100 parts of oak gall, for In the presence of 0.1 to 8.0 parts by weight, it may take up to 8 hours to complete or. The present invention also includes the use of the anti-return ribbing agent of formula A in the sulfur-vulcanization process of the standard:% Λ 6 η 6 V. Description of the invention () Finally, the present invention also includes the preparation of articles. Such as tires, It contains sulfur-vulcanized rubber under vulcanization of the anti-return auxiliary adjuvant in formula A. The present invention is further illustrated by the following examples, but it is not intended to limit the scope of the invention. The scope of the present invention can be determined by the scope of subsequent patent applications. The H-NMR spectrum was recorded by Brukei: W P 2 0 0 S Y using TMS as the internal standard. Example 1 萑 鹹 2 _ cis-methylbutene dibenzimidimide ethyl) disulfide synthesis in 28. 1 5 grams desamine diimide (cystamine) 2 HC 1 and 22 grams of vinegar 1 5 ΟmL xylene in M mixed slurry. Add 28.10 g of icitraconic anhydride. Heat and reflux the mixture, and accumulate the formed water in the Dea η-S tark device. When the water is no longer formed, cool the slurry, and in case of removal to remove the class 5 Distill the clear solution under vacuum to remove dimethanone: . The resulting viscous dark oil (4 1.5 g) crystallized slowly under standing. After recrystallization from ethanol, an opalescent product with a melting point of 5.2 can be obtained. From Η (please read the precautions first and then fill out this page) Employee Consumers of the Ministry of Economic Affairs, Bureau of Standards & Co., Ltd. Co-printed N MR data to identify the ethyl imine produced in this product) Disulfide:
頭式甲基丁烯二S 實施例2 雙(4 -順式甲基丁烯二顏亞胺苯基)二硫化物之合成 在3 1克ρ , ρ —二胺基二苯基二硫化物於1 5 0 _-15- _ Κ紙張尺度边用中國困家樣準(CNS) ΤΜ規格(210X297公龙) 2〇9冰 五、發明説明() 毫升之二甲苯的攪拌漿液中加入2 8. 1克之擰康酐。加 熱迴流混合物,並將所形成之水積於Dean-Stark装置中。 於停止形成水後,冷卻漿液,並過濾以去除産物,再以二 甲苯冲洗冲兩次。將産物(48. 6克)於真空下乾燥。 由Η — NMR可知所得産物為雙一 (4 —順式甲基丁烯二 藝亞胺苯基)二硫化物。 (請先閲請背而之注意事項洱塥寫本頁) 烯 丁 基 甲 式 順 I 2 雙 3 1 例 2 施’ 實 1 乙 製於 所烷 序 乙 程 -之 > 述代 所硫 7 基 1 苯 6 基 . 胺 ο - 2 2 9 丨 , 雙 3 _ 利 2 專 -國 1 美克 昭I ο 成依 ο 合 在 1 之 之 烷 備 康装去 擰rk以 之tais 克-S蒸 6aη下 1D8空 . 於真 1 積於 8 水並 λ 之液 加成溶 中 形卻 夜 所 今' .,·(11 1L 1!. \ Τ. 溶將 , 拌 並 凌 S,之 之物水 基 合成 甲混形 二 流止 升 迴淳 毫¾在 ο 加 。 LO 中 3 酐置 裝· 訂 線_ 經濟部中央榀準局员工消伢合作杜印鲅 1 垸 1 為 乙 ,1,¾_ 油産 — 暗知代 稠可硫 黏 R* 之 Μ 苯 荨 Ν 安 //1 Φ(1 所一亞 .i~s --rtr ;.·= 苯由 二 甲 :_ 二 化 丁 除固 1一 基 甲 4 式 洌順 施 I 實 2 克 3 6 2 的 甲 慢式 缓順 將 - 時 2 置 ,—' 靜雙 醒I 三 烯 丁 基 甲 式 II - 2 - 基 苯 胺 亞 所 序 程 之 述 所 4 7 5 4 3 7 2 E 成 D 合利 之 專 物國 化德 硫照 基依 乙在 胺 亞 本紙張尺度边用中困Η家標準(CNS)T4規格(210x297公龙) 9.09:Head-type methylbutene di S Example 2 Synthesis of bis (4-cis-methylbutene diimide phenyl) disulfide at 31 g ρ, ρ-diaminodiphenyl disulfide On the 1 5 0 _-15- _ κ paper scale side, use the Chinese trapped home standard (CNS) TM specifications (210X297 male dragon) 2〇9 冰 五. Invention description () Add 2 8 milliliters of xylene to the stirring slurry . 1 gram of Xuankang anhydride. The mixture was heated to reflux, and the formed water was accumulated in the Dean-Stark apparatus. After stopping the formation of water, the slurry was cooled and filtered to remove the product, and rinsed twice with xylene. The product (48.6 g) was dried under vacuum. It can be known from H-NMR that the resulting product is bis- (4-cis-methylbutenediiminephenyl) disulfide. (Please read the notes on the back of Erzhen to write this page) Allyl methyl cis-I 2 double 3 1 Example 2 Shi 'Shi 1 Shi system in the order of the alkyl group->> Describe the sulfur 7 base 1 Benzene 6 base. Amine ο-2 2 9 丨, double 3 _ 利利 2 special-country 1 Meike Zhao I ο Cheng Yi ο combined in 1 of the alkane prepared equipment to screw rk to tais g-S steam 6aη under 1D8 Empty. Yu Zhen 1 accumulates in 8 water and the liquid of λ is added to dissolve, but the shape of the night is now '., · (11 1L 1 !. \ Τ. Rongjiang, mix with Ling S, water-based synthetic armor Mixed second-rate stop rising back to the pure ¾ in ο add. LO in 3 Anhydride installation · line _ Central Ministry of Economic Affairs of the Ministry of Economic Affairs staff cooperation cooperation Yinyue Duan 1 Embankment 1 is B, 1, ¾_ Oil production-Anzhizhidai Thiosulfur sticky R * of M benzene net ampere // 1 Φ (1 Soyiya.i ~ s --rtr;. · = Benzene by dimethyl: _ dibutylene in addition to solid 1 monomethyl 4 type Xuan Shunshi I Shi 2 grams of 3 6 2 of the slow-slow-on-set of the slow-time 2 set,-'Jing Shuangxing I Trienebutyl Form II II-2-Phenylaniline Subsequence 4 7 5 4 3 7 2 E Dedicated to the D of Heli Alkylene amine acetate groups by the present specification sheet side with the scales of T4 trapped Η of Standards (CNS) (210x297 male Long) 9.09:
Si Λ 6 II 6 經濟部屮央櫺準局员工消许合作杜印製 五、發明説明() 製備之50克2 — (2 —胺基苯基硫代)一乙烷胺於25 0毫升之二甲苯的橿拌溶液中加入67. 2克之檸康酐。 加熱迴流混合物,並將所形成之水積於Dean-Stark裝置中 。在停止形成水之後,冷卻溶液並於真空下蒸餾以去除二 甲苯。所得之黏稠暗色油(1 0 3 . 5克)在靜置後緩慢 地固化。由H — NMR可知産物為2 —順式甲基丁烯二g 亞胺苯基一 2 —順式甲基丁烯二醯亞胺乙基硫化物。 實施例5 1 , 4 —雙(2 _順式甲基丁烯二截亞胺苯基硫代)一丁 烯一 2之合成 在依照美國專利3 , 9 2 0. 6 1 7中所述之程序所 製備之1 2 5克之1 , 4 —雙ί 2 _胺基苯基硫代)—2 一 丁烯於3 5 0毫升之二甲苯的擬拌溶液中加人9 2 . 7 4克之擰康酐。加熱並迴流混合物,並將所形成之水積在 D e a η - S t a r k裝置中:,在停止形成水之後,冷卻溶丨夜並於真 空下蒸餾以去除二甲苯。所得之黏稠暗色油(1 9 3克) 在靜重+ί+曼邊慢画化;.由Η — N M R可知所得産物為1 , 4 —雙(2 —順式甲基丁烯二醯亞胺苯基硫代)一丁烯一2 實施洌6 m (2 —順式甲基丁烯二蟊亞胺苯基)一二硫化物之合 表紙張尺度边用中as家槔率(CNS)T4規格(210x297公:¢) (請先閲讀背而之注意事項#塡寫本頁) Λ 6 Β 6 經求部中央榀準局工消费合作社印¾ 五、發明説明() 成 在1 00克2 —胺基苯基二硫化物於350毫升二甲 苯中之部分溶解攪拌漿液中加入90. 9克之檸康酐。加 熱迴流混合物.並將所形成之水積於Dean-Stark裝置中。 在停止形成水之後,將溶液冷卻至室溫。過濾以去除固體 ,以100毫升二甲苯冲洗二次,並於真空下乾燥,可産 生熔點為1 85. 5 — 1 87 °C之乳色産物59. 9克。 合併二甲苯部分,並於真空下去除二甲苯。於3 0 0毫升 乙醇中迴流所得之黑色油。將乙醇溶液冷卻至5 t ,並過 濾以除去固體,於真空下乾燥可獲得熔點185. 5 - 1 8 6 . 8 t'之頷外産物1 4 . 4克,:,由Η — N M R可知此 二産物為雙一 (2 —頃式甲基丁烯二諉亞胺苯基)二硫化 物C, 實施_ 7 - 1 1和[:b較實施例A 天然頌P化合物:在以五種不同式A之輔肋_硫化之天然 橡®化会物之Μ ο n s a η ΐ q R h e ◦ g r a 3 s之殘留力矩ί t ο r g u e r 3 l e n : ; ο n ; 基本化合物(化合物A =對照) N R : S M R C V 5 1 0 0 份 石黃黑 N330 5 0 p h r 硬脂酸 2 p h r 氧化鋅 R S 5 p h r (請先閲讀背而之注意事項#堝寫本頁) 裝· 線. 本紙5fc尺度边用中8 8家標準([奶)174規格(210父297公逢)" 五、發明説明( Λ 6 15 6 @ D U t r e X 7 2 9 HP 3 Ρ h Γ C B S 0 . 6 Ρ h Γ 硫 2 . 3 Ρ h Γ 經濟部中央楛準局员工消伢合作杜印製 用作試驗含聚順式甲基丁烯二醒亞胺之(聚)硫化物: 1 .雙(2 -順式甲基丁烯二鏗亞胺笨ϋ )二硫化物(Β C I - ο P h 2 ) :) 2. 雙P4-順式甲基丁烯二鏜亞胺^苯基硫代0乙烷、(B ' 1 C I - P T E ) 一 ' 3. 雙(2 —順式甲基丁烯二醛亞胺笨,基硫代.!:乙烷(B C I - Ο P T E ) ' ’ 4. 雙(2 —順式甲基丁烯二證亞胺έ基)二硫化物(Β C I - Ξ S 2 ) - - 5. 雙(4—順式甲基丁烯二證亞胺苯基)二硫汜物< Β C I - ρ h 2 ) , - r 化合:B a n b u r* y 1 . 6升,7 0 %負載偽數,7 _7 r p m ,起始温度5 Ο Γ ,混合時間6分鐘;兩輪壓碎 機ί硫化割W S C I i : S碧擦i : I . 2 Σ ,起始品 度4 0 — 5 0 € , 3分篷。 硫化曲線:Monsanto Rheometer MDR 2000E,弧度 0. 5 度,溫度1 7 0 5C和1 8 0 t ,至6 0分鐘。%殘留力矩 為硫化曲综之最終力矩除以最大力矩(如表1 !:, ν3 , (請先閲讀背而之注意事項再填寫本頁) 裝. 線_ t紙張尺度边用中困S家楳準(CNS)TM規格(210X297公¢) 66 An 2,0¾ 五、發明説明() 表- 實施例# BCI 濃度 ,溫度 時間 ......... %殘留力矩 -- phr °c .'分 (對照_| oPii2 1*0 :170 30 86 (74) .^ PT2 1.1 170 60. 87 |(71) OPTS 170 50 81 b〇) .r *ES2 1.7 180 60 123 1(65) Ph2 2.2 130 60 119 |{66 ) i 含聚頃式甲基丁烯二證亞胺之(聚)硫化物在相當高 之溫度下過度熟化後,與對照組比較顯示具改善之殘留力 矩,表示含有聚順式甲基丁烯二醯亞胺之(聚)硫化物具 改善之抗返原性質 (請先閲讀背而之注意事項#塡寫本頁) 裝· T -5 - 線- 經濟部中央捣準而3工消"合作杜印5i 實施剠1 2 — 1 3和比較實強例B 天Μ滢獲Ml;合均:疏! t抟忿钼性質:壓Η藉由於 和1 8 0 t下Μ縮模製而碕化,並分別最適熟化 )和過度熟化3 0分鐘和6 0分鐘3 試驗方法: 2g ~h I S 0 3 7 / 2 -啞鈐 本紙張尺度边用中S困家標準(CNS)干<1規格(210x297公龙) rr η γ> t 9 Ο Ί Λ 6 Π 6 五、發明説明 斷裂時之伸長悬:ISO 37/2-啞鈐 模數 硬度 彈性 壓縮變形Si Λ 6 II 6 Employee of the Central Bureau of Economics of the Ministry of Economic Affairs has allowed cooperation to print Du. Fifth, the description of invention () 50 g of 2-(2-aminophenylthio) monoethylamine prepared in 250 ml 27.2 grams of citraconic anhydride was added to the xylene stir solution. The mixture was heated to reflux, and the formed water was accumulated in the Dean-Stark apparatus. After stopping the formation of water, the solution was cooled and distilled under vacuum to remove xylene. The resulting viscous dark oil (1,03.5 g) solidified slowly after standing. It can be known from H-NMR that the product is 2-cis-methylbutene dig imine phenyl- 2-cis-methylbutene diimide ethyl sulfide. Example 5 1, 4-bis (2- cis-methyl butene bis-imino phenylthio)-butene-2 synthesis according to US Patent 3, 9 2 0. 6 1 7 The procedure prepared 1 2 5 grams of 1, 4-bis ί 2 _ aminophenyl thio))-2 monobutene in 3 500 ml of xylene in the mixed solution was added with 9 2. 7 4 grams of screw Kang anhydride. The mixture was heated and refluxed, and the formed water was accumulated in the De a η-S t a r k device: After the formation of water was stopped, the solution was cooled and distilled under vacuum to remove xylene. The resulting viscous dark oil (193g) was slowly drawn on static weight + ί + Mann ;; Η-NMR shows that the resulting product is 1, 4-bis (2-cis-methylbutene diimide) Phenyl thio) -butene-2 implementation of 6 m (2-cis-methylbutene dicarboximine phenyl) -disulfide combined surface paper used in the paper scale rate (CNS) T4 Specifications (210x297 g: ¢) (please read the notes beforehand # 塡 write this page) Λ 6 Β 6 Printed by the Ministry of Economic Affairs, Central Bureau of Industry and Commerce Cooperative Cooperative ¾ V. Description of invention () into 1 00 g 2 9 克 的 citraconic anhydride was added to the partially dissolved stirring slurry in 350 ml of xylene in aminophenyl disulfide. The mixture was heated to reflux. The formed water was accumulated in the Dean-Stark device. After stopping the formation of water, the solution was cooled to room temperature. 9 克。 Filtered to remove solids, washed twice with 100 ml of xylene, and dried under vacuum, can produce a melting point of 18.5 5-1 87 ° C milky product 59.9 grams. The xylene fractions were combined and xylene was removed under vacuum. The resulting black oil was refluxed in 300 ml of ethanol. The ethanol solution was cooled to 5 t, and filtered to remove solids, dried under vacuum to obtain a melting point of 185.5-18.6 6 t's of the external product 14.4 grams ,: Η-NMR can know this The second product is bis- (2-hexylmethylbutene diiminophenyl) disulfide C, implemented _ 7-1 1 and [: b compared to Example A natural sulfonate P compound: in five different Auxiliary rib of formula A_M ο nsa η Ι q R he ◦ of vulcanized natural rubber® compound □ residual moment of gra 3 s t t ο rguer 3 len:; ο n; basic compound (compound A = control) NR : SMRCV 5 1 0 0 parts yellow yellow black N330 5 0 phr stearic acid 2 phr zinc oxide RS 5 phr (please read the back-to-back precautions ## to write this page) pack · line. The paper 5fc standard side use 8 8 standards ([milk] 174 specifications (210 father 297 public meeting) " V. Description of invention (Λ 6 15 6 @ DU tre X 7 2 9 HP 3 Ρ h Γ CBS 0.6. Ρ h Γ sulphur 2. 3 Ρ h Γ The Ministry of Economic Affairs, the Central Bureau of Economic Cooperation, employees cooperated with Du Printing to test (poly) sulfide containing polycis-methylbutene divinyl imine: 1. bis (2-cis Butyl butene diethylenimine) disulfide (B CI-ο P h 2) :) 2. Double P4-cis-methylbutene diboron imine ^ phenylthio 0 ethane, (B '1 CI-PTE) one' 3. bis (2-cis-methylbutadiene diimide, stupid, thiothio.!: Ethane (BCI-Ο PTE) '' 4. bis (2-cis Methylbutene diethylenimine disulfide (B CI-Ξ S 2)--5. Bis (4-cis-methylbutene diethylenimine phenyl) disulfide dihydrate <B CI-ρ h 2),-r compound: B anbur * y 1.6 liters, 70% load pseudo-number, 7 _7 rpm, initial temperature 5 Ο Γ, mixing time 6 minutes; two-wheel crusher vulcanization Cut WSCI i: S Bishuang i: I. 2 Σ, starting grade 4 0-50 0 €, 3 points canopy. Vulcanization curve: Monsanto Rheometer MDR 2000E, arc degree 0.5 degree, temperature 1 7 0 5C and 18 0 t, to 60 minutes. The% residual torque is the final torque of the vulcanized curved heald divided by the maximum torque (as shown in Table 1!:, Ν3, (please read the precautions before filling in this page) to install. Thread_ t Standard (CNS) TM (210X297 g) 66 An 2,0¾ V. Description of the invention () Table-Example # BCI concentration, temperature time ...% residual moment-phr ° c . 'Points (control_oPii2 1 * 0: 170 30 86 (74). ^ PT2 1.1 170 60. 87 | (71) OPTS 170 50 81 b〇) .r * ES2 1.7 180 60 123 1 (65) Ph2 2.2 130 60 119 | {66) i After the poly (sulfide) sulfide containing poly (methylbutene diethylenimine) is over-ripe at a relatively high temperature, it shows an improved residual torque compared with the control group, indicating that it contains The (poly) sulfide of polycis-methylbutene diimide has improved anti-return properties (please read the back-to-back precautions # 塡 write this page) 装 · T -5-Line-Central Ministry of Economic Affairs Punctuation and 3 work elimination " Cooperative Du Yin 5i implementation 剠 1 2 — 1 3 and comparatively strong example B days M won the Ml;抟 忿 Molybdenum properties: Pressed by shrinkage molding with M under 180 t, and optimally matured respectively) and over-cured for 30 minutes and 60 minutes 3 Test method: 2g ~ h IS 0 3 7 / 2-Dumb-printed paper standard-side medium-sleepy standard (CNS) dry < 1 specification (210x297 male dragon) rr η γ > t 9 Ο Ί Λ 6 Π 6 V. Description of the invention Elongation at break: ISO 37 / 2-dumb dull modulus modulus elastic compression deformation
:ISO 37/2-啞鈐 :ISO 48CIRHD)或 DIN 53505(Shore A) :ISO 4662 :玉 S 0 R δ 1 5 ; 7 2 小時於 2 3 °C 分別測定實施例1 0和1 1所製備化合物之機械性質,並 旦與對照之實施例Β比較(表2和3 ) 〇 表2 —於1 5 0 r硫化以適窆熟化(3 0分撞後)之化会 物的物理和機娀性質 (請先閲讀背而之注意事項再塡寫本頁) 經濟部中央櫺準局貝工消伢合作社印製 測 試 B(Η 〇 BCI) 12 (BCI-ES2) 1 3 ( B C I - P h 2 ) 硬度(I R H D) 7 0 7 0 7 5 張力(Μ P a ) 2 7.3 21.2 2 7.4 伸長量(% ) 4 90 5 0 0 4 90 模數 5 0 Η P a ) 1 . 6 1.6 1.9 mm ίο ο % (H F a ) 3 . 2 3 . 2 3.7 漠數」0 ,¾ ί. Η P a ) I 6 . i i 5 . 7 15.3 反彈彈性(s) 3 6 3 6 35 壓縮變形 1 1 1 1 15 表3 —於1 8 0 3C下硫化1 小時之化合物的 物理和機械性 質 0 1 _ 良紙5fc尺度边用中a S家楳準(CNS) T4規格(210X297公放) 經濟部屮央榣準局员工消t合作杜印製 五、發明説明() 測 試 硬度(IRHD) 張力(MPa) 模數 50¾ (MPa) 模數 1 0 0 U Η P a ) 模數 3 0 G 2 (Μ P a) 反彈彈性(3;) 壓縮變形(S) Λ 6 Π 6 BCI) 12 (BCI-ES2) 13 (BCI -Ph2) 60 7 2 78 17.0 2 2.5 17,9 1.1 1.9 2.6 1 . 8 9.2 3.9 2 0.2 5,2 3 1 35 3 2 2 0 12 19 (請先閲讀背而之注意事項#堝寫本頁) 裝. 含BC I ^ES2和BC I — Ph2之化合物在相當 高溫(180=0)溫度熟化浚,與對照組比較,頸示具有 實質改進之機域性質:較高硬度,張力,模數和彈控,以 及較低之壓縮變形:, 實施例1 4和比較實施钶C 卡車镝眙眙面化合物 卡車輪眙化合物包含以半一 E . V熟化条统熟化之N R / B R t〇 ; 50 C.S.l. Eaksr#A K Eiastoserics, 1989七月,pp. 20所述,參見以下配方)者與BC I — E S 2 —起裂備。 配 方 成 份 NR SMR 20 14 8 0.00 3 0.00 線· 本紙张尺度逍用中8 8家標準(〔卟)'?4規怙(210><297公;《:) 五、發明説明() Λ 6 Η 6 B R Buna CB 10 20.00 20.00 磺黒N - 3 7 5 55.00 55.00 硬脂酸 2.00 2.00 氣化鋅R S 4.00 4.00 芳族油D u trex 729 HP 8,00 8.00 Pernansx 6PPD 2.00 2.00 BCI - ES2 1.00 - Parkscit CBS c 1.20 1.20 硫 1.20 1.20 (請先閲讀背而之注意事項#塡寫本頁) 經试部中央榀準局Α工消赀合作社印51 化合:B a n b u r y 5 . 0升,7 0 %負載偽數,4 0 r p m ,起 始溫度5 0 t:,混合時間6分逵;兩輪壓碎(硫化割和B C I ):滾壓磨擦1 : 1_ 22,起始溫度40 — 50t .3分鐘。壓片傜Μ由在150和170 t壓縮塑漠而硫 it ,以分別使之最適熟化i t 9 0 )和過度熟化6 0分鐘 及3 0分鐘。 除了上述之外的試驗方法: Mooney 黏度 :ISO R-Wii-HLlOOl' Kooney過度硫化:ISO R-2S3-ML121=C 流變性質 :Μ ο n s a n t ο M D E 2 Ο Ο Ο E 彈性 :I S Ο 4 6 6 2 抗扯性 :I S Ο 3 4 - 1毫米之新月形切口 磨蝕性 :D I Ν 5 3 . 5 1 S ___^ Λ 本紙法尺度边用中8 8家楳準(〇胳)〒<1規格(210父297公:4〇'1 Λ (5 Β 6 五、發明説明I 熱空氣熟化 壓縮變形 停止疲乏 :I S 0 1 8 3 -於 1 Ο Ο π 1 和 3 天 :I S 0 R 8 1 5 ;於 2 3 它 1 天 :A S T M D 4 4 8 2 / c a m 2 4 / 8 個樣品 G ο o d r i c h 撓曲計:A S T H D 6 2 3 A / T 起始 1 Ο 0 / 3 Ο Η z 此外,流變性質偽於許多不同時間和溫度,使用2 . 5 N m之範圍和0 . 5度之弧度測量。B C I - E S 2 在蘑用上對Mo ο n e y黏度和過早硫化時間並無任何影 鎏(表4 ),表5領示了在不同溫度之熟化待歡,:, (請先閲讀背而之注意事項再塡寫本頁) 經濟部中央槛準局员工消伢合作杜印奴 表4 性質 _照;c Μ ο ο n s y 站度 4 6.4 過早硫化時間 36.1 表5 Η ο n a s n t 〇流度計熱ΐ數S 溫度:I 4 ϋ C t s 2 (分鐘) β力矩ί N m ) 溫度:1 8 o r t s 2 ί分鐘) <5 力矩(N rn 1 B C I - E S 2 ( 1 4 ) 44.9 3 5.1 對照 10.1 • 53 S 2 ( 1 4 10 .45 .95 .23 t紙張尺度边用中a a家標準(CHS) TM規格(210X297公龙) Λ 6 IJ 6 經濟部中央標準局CX工消仲合作杜印51 五、發明説明() 表6表由Monsanto流度計於1 4 0 °C ,在多至8小時 之延長熟化時間所測定之熟化曲線而得之殘留力矩。B C I_ES2對橡膠之返原具實質之(過度)補傖效應。 表6 殘留力矩 (% ) 對照(c ) 7 7 B C I - E S 2 (14) 121 表7表於1 5 0和1 7 0 t過早熟化後之硫化産物在 不同性質之改善:改進之硬度,反彈彈性.張力,模數, 磨蝕性,抗扯強度,組会之熱和永久變形:,伸長量,壓縮 變形和疲乏並無實質之改變:所得之值偽最適熟化時之值 ,括弧内之值為1 5 0 :C:下6 0分鐘熟化和1 7 0 3C下3 ◦分鐘化之值,: rfci —} f •TJiI 5—U i^J 6Λ 硬度(I R H D) c 14 c 14 (無 BCI) (BCI-ES2)(無 SCI) (BCI-ES2) 70 70 69 68 (67) (72) (S3) (70) 本紙張尺度边用中a租家標準(CNS) T4規格(210x29/公) (請先閲讀背而之注意事項洱填寫本頁) Λ 6 I? 6 五、發明説明() 張力 (MPa) 25.5 25.0 (21.9) (23.1) 伸長量(¾) 25.1 24.5 (16.8) (22.3) 模數 5 Q U Μ P a ) 模敦 100¾ (MPa) 經濟部中央標準局β工消赀合作杜印製 模數 30!U(MPa) 1 (1 磨註性(3 Η 3 ) 小時,2 3 t ( 0 550 580 600 0) ( 4 6 0 ) ( 5 3 0 ) (5 0 0 ) 2 1.2 1.2 1.1 1) (1.4) (1.0) (1.3) 4 2 . 1 2 . 1 1 . 9 η ·. 3 / (2 . S ) (1.5) !: 11.9 11,2 10.0 .5; (13.7) (7.6) (1 1 . 4 3 2 3 0 8 3 9 6 1 1 Λ 1 Λ .Λ ▲ 一· Μ X w · 4.5) (13.1) (17.5) (12.2) 115 1 0 3 10 5 10 9 (83 ) (100) -23- (43) (72) (請先閲讀背而之注意事項#塡寫本頁) 裝· 線- 衣紙張尺度边用中a困家標準(CNS) Ή規格(210X297公龙) Λ 6 Π 6 五、發明説明() 永久變形(%) 組成熱(t:) 13.1 10.1 (13.9) (5.4) +40 +27 (+47) (+25) 14.0 13.4 (17.9) (6.6) +39 +29 (+58) (+27) (請先閲讀背而之注意事項#填寫本頁} 包含B C I — E S 2之化合物與對照化合物在熟化後性質 改善之比較亦記錄於表8及9。 表8 — 1 5 0 t,最適熟化之橡啜經2 4及7 2小時 熟化.且括弧内為熟化1 5 0 t . 6 0分鐘己熟化橡2 4及7 2小時之值。所有之熟化均於1 〇 〇 f下進行。 裝. 訂 線. 表8 測試 經试部中央榀準局CX工消赀合作社印¾ 硬度 2 4小時 c 14 (無 S C 工)(B C I,E S 2 ) 7 4 7 4 2小時 4: ISO 37 / 2-dumb: ISO 48CIRHD) or DIN 53505 (Shore A): ISO 4662: Jade S 0 R δ 1 5; 7 2 hours at 2 3 ° C were prepared by measuring Examples 10 and 11 respectively The mechanical properties of the compound are compared with the control example B (Tables 2 and 3). Table 2-Physics and mechanical properties of chemical compounds cured at 1 50 r to cure (after 30 minutes) Nature (please read the precautions before writing this page) Printed Test B (Η 〇BCI) 12 (BCI-ES2) 1 3 (BCI-P h 2 ) Hardness (IRHD) 7 0 7 0 7 5 Tension (Μ P a) 2 7.3 21.2 2 7.4 Elongation (%) 4 90 5 0 0 4 90 Modulus 5 0 Η P a) 1. 6 1.6 1.9 mm ίο ο % (HF a) 3. 2 3. 2 3.7 desert number ″ 0, ¾ ί. Η P a) I 6. Ii 5. 7 15.3 rebound elasticity (s) 3 6 3 6 35 compression deformation 1 1 1 1 15 Table 3 —Physical and mechanical properties of compounds vulcanized at 180 ° C for 1 hour. 0 1 _ Good paper 5fc scale edge-use medium a S Jiayu standard (CNS) T4 specifications (210X297 public release) Biyang Bureau of Economic Affairs, Ministry of Economic Affairs Employee dissipation cooperation Du Du V. Invention description () Test hardness (IRHD) Tension (MPa) Modulus 50¾ (MPa) Modulus 1 0 0 U Η P a) Modulus 3 0 G 2 (Μ P a) Rebound elasticity (3;) Compression deformation (S) Λ 6 Π 6 BCI) 12 (BCI-ES2) 13 (BCI -Ph2) 60 7 2 78 17.0 2 2.5 17,9 1.1 1.9 2.6 1. 8 9.2 3.9 2 0.2 5,2 3 1 35 3 2 2 0 12 19 (please first Read the back-and-attention notes #Crown to write this page) installed. The compound containing BC I ^ ES2 and BC I — Ph2 is matured at a relatively high temperature (180 = 0). Compared with the control group, the neck shows a substantial improvement Domain properties: higher hardness, tension, modulus and elasticity control, and lower compression deformation :, Example 14 and comparative implementation of holmium C truck dysprosium surface compound truck wheel squat compound contains half-one E. V ripening NR / BR t〇 of the aging system; 50 CSl Eaksr # AK Eiastoserics, July 1989, pp. 20, see the following formula) and BC I-ES 2-cracking equipment. Formulation Ingredients NR SMR 20 14 8 0.00 3 0.00 Line · This paper standard is used in 8 of 8 standards (〔訓) '? 4 regulations (210> < 297 public; ":) V. Description of invention () Λ 6 Η 6 BR Buna CB 10 20.00 20.00 Sulfur N-3 7 5 55.00 55.00 Stearic acid 2.00 2.00 Vaporized zinc RS 4.00 4.00 Aromatic oil D u trex 729 HP 8,00 8.00 Pernansx 6PPD 2.00 2.00 BCI-ES2 1.00-Parkscit CBS c 1.20 1.20 Sulphur 1.20 1.20 (please read the back-to-back notes # 塡 write this page first) The Central Bureau of Examination of the Examination Department A Gong Xiao Zheng Cooperative Seal 51 Compound: Banbury 5.0 litres, 70% load pseudo Number, 40 rpm, initial temperature 50 t :, mixing time 6 minutes; two rounds of crushing (vulcanization and BCI): rolling friction 1: 1-22, initial temperature 40-50t. 3 minutes. Compressed tablets are compressed at 150 and 170 t, so as to make them the most suitable for maturation (i t 9 0) and over-maturation for 60 minutes and 30 minutes, respectively. Test methods other than the above: Mooney Viscosity: ISO R-Wii-HL100l 'Kooney Overvulcanization: ISO R-2S3-ML121 = C Rheological properties: Μ ο nsant ο MDE 2 Ο Ο Ο E Elasticity: IS Ο 4 6 6 2 Tear resistance: IS Ο 3 4-1 mm crescent-shaped incision Abrasiveness: DI Ν 5 3. 5 1 S ___ ^ Λ In this paper, the standard scale is used in 8 8 楳 樳 准 (〇) 〒 < 1 Specification (210 father 297 males: 4〇'1 Λ (5 Β 6 V. Description of invention I Hot air aging compression deformation stops fatigue: IS 0 1 8 3-at 1 Ο Ο π 1 and 3 days: IS 0 R 8 1 5; on 2 3 it 1 day: ASTMD 4 4 8 2 / cam 2 4/8 samples G ο odrich flexometer: ASTHD 6 2 3 A / T start 1 Ο 0/3 Ο Η z In addition, flow The change of properties is pseudo at many different times and temperatures, using a range of 2.5 N m and an arc of 0.5 degrees. BCI-ES 2 has no influence on Mo ney viscosity and premature vulcanization time in mushroom application. (Table 4), Table 5 shows the maturation at different temperatures, please: (Please read the notes before writing and then write this page) Employees of the Central Bureau of Economic Affairs of the Ministry of Economic Cooperation and Cooperation Du Yinnu Table 4 Nature_photo; c Μ ο ο nsy station degree 4 6.4 premature vulcanization time 36.1 Table 5 Η ο nasnt 〇 fluidometer heat number S temperature: I 4 ϋ C ts 2 (min) β moment ί N m) Temperature: 1 8 orts 2 minutes) < 5 Torque (N rn 1 BCI-ES 2 (1 4) 44.9 3 5.1 Contrast 10.1 • 53 S 2 (1 4 10 .45 .95 .23 t paper scale in use aa family standard (CHS) TM specification (210X297 male dragon) Λ 6 IJ 6 Central Ministry of Economic Affairs CX Gongxianzhong cooperation Du Yin 51 V. Description of invention () Table 6 Table 1 by Monsanto fluidity meter 1 4 0 ° C , The residual torque obtained from the curing curve measured by the extended curing time of up to 8 hours. BC I_ES2 has a substantial (excessive) compensation effect on the reversion of the rubber. Table 6 Residual torque (%) Control (c) 7 7 BCI-ES 2 (14) 121 Table 7 shows the improvement of different properties of the cured products after premature aging at 150 0 and 1 70 t: improved hardness, rebound elasticity, tension, modulus, abrasiveness, resistance Tear strength, heat and permanent deformation of the assembly: There is no substantial change in elongation, compression deformation and fatigue: the value obtained is pseudo-optimal The value in parentheses is 1 5 0: C: aging under 60 minutes and 3 7 minutes under 1 7 0 3C: rfci —} f • TJiI 5—U i ^ J 6Λ Hardness (IRHD) c 14 c 14 (without BCI) (BCI-ES2) (without SCI) (BCI-ES2) 70 70 69 68 (67) (72) (S3) (70) This paper scale is used in the standard a renter standard (CNS ) T4 specification (210x29 / cm) (please read the precautions first and fill in this page) Λ 6 I? 6 V. Description of invention () Tension (MPa) 25.5 25.0 (21.9) (23.1) Elongation (¾) 25.1 24.5 (16.8) (22.3) Modulus 5 QU Μ P a) Modun 100¾ (MPa) The Ministry of Economic Affairs Central Bureau of Standards β-work consumer cooperation cooperates to print the module 30! U (MPa) 1 (1 grindability ( 3 Η 3) hours, 2 3 t (0 550 580 600 0) (4 6 0) (5 3 0) (5 0 0) 2 1.2 1.2 1.1 1) (1.4) (1.0) (1.3) 4 2. 1 2. 1 1. 9 η ·. 3 / (2. S) (1.5)!: 11.9 11, 2 10.0 .5; (13.7) (7.6) (1 1. 4 3 2 3 0 8 3 9 6 1 1 Λ 1 Λ .Λ ▲ 1 · Μ X w · 4.5) (13.1) (17.5) (12.2) 115 1 0 3 10 5 10 9 (83) (100) -23- (43) (72) (Please read first Notes on the back # 塡 write this page) 装 · 线-衣 纸Standards for the use of scales (CNS) Ή specifications (210X297 male dragon) Λ 6 Π 6 V. Description of invention () Permanent deformation (%) Composition heat (t :) 13.1 10.1 (13.9) (5.4) +40 + 27 (+47) (+25) 14.0 13.4 (17.9) (6.6) +39 +29 (+58) (+27) (please read the back-end notes #fill this page} contains BCI-ES 2 compounds The comparison of the property improvement with the control compound after aging is also recorded in Tables 8 and 9. Table 8-1 50 t, the most suitable rubber slurries matured after 2 4 and 7 2 hours. And the parenthesized in the brackets are the values of matured rubber 2 4 and 7 2 hours. All aging is carried out at 100 f. Binding. Threading. Table 8 Tested by the Central Examination Bureau of the Ministry of Testing, printed by the CX Gongxiao Cooperative Society ¾ Hardness 2 4 hours c 14 (without S C workers) (B C I, E S 2) 7 4 7 4 2 hours 4
(無 BCI) (BCI-ES (7 0 2) (5 8) (74) 張力 (MPa) 26.0 25.8 (20.1) (24.6: 21.4 22.8 16.7) (19.S) 本紙張尺度逍用中as家標準(CNS)TM規格(210x297公:《:) - 五、發明説明() Λ 6 15 6 模數 503: (MPa) 1 . δ 1.7 (1.4) (1.8) (1.5) (2.1) 模數 lOOUMPa) 3.5 3.5 (2.5) (3.6) C2.8) (4.2) 模數 3003UMPa) 16.4 16.0 (12.0) (16.9) 16.0 16.8 (12.5) (17.6 表9_ 1 7〇iC,經最適熟it之橡穋熟化24和72小時 .且括弧内為1 7 0 t , 3 0分鐘熟化之橡膠熟化2 4及 7 2小時之值。所有熟化均於1 0 ◦ =C下進行。 表9 測試(Without BCI) (BCI-ES (7 0 2) (5 8) (74) Tension (MPa) 26.0 25.8 (20.1) (24.6: 21.4 22.8 16.7) (19.S) This paper standard is used in the As standard (CNS) TM specification (210x297 g: ":)-V. Description of invention () Λ 6 15 6 Modulus 503: (MPa) 1. δ 1.7 (1.4) (1.8) (1.5) (2.1) Modulus lOOUMPa) 3.5 3.5 (2.5) (3.6) C2.8) (4.2) Modulus 3003UMPa) 16.4 16.0 (12.0) (16.9) 16.0 16.8 (12.5) (17.6 Table 9_ 1 70iC, matured by the most suitable it oak 24 And 72 hours. And the parenthesis is 1 70 t, 30 minutes of rubber maturing value of 2 4 and 7 2 hours. All curing is carried out at 1 0 ◦ = C. Table 9 Test
2 4小時 7 2小時 c 14 c 1 4 (無 S C I ) ( B C I - E S 2 )(無 B C I) ( B C I - E S (請先閱讀背而之注意事項再项窍木頁) 裝· 打_ 線· 經濟部中央櫺準局Μ工消赀合作杜印¾. 65 (67) (73) 張力 (MPa) 25.3 25.5 2 0.2 20.1 (15.6) (21.1) (12.9) (17.1) 本紙張尺度边用中國a家標準(CNS)1?*!規格(210x297公逢) 2 〇9 Λ 6 li 6 五、發明説明() 模數 502(MPa) 1.7 1.7(1.2) (1.6) 1.4) 1.9(1.9) 模數 lOOUHPa) 3.4 3.3 (1.9) (2.9) 2.3) (3.5) 模數 3 0 0 UMPa) 15.8 15.5 (9.0)(14.2) 15.5 16.2 (9.8) (15.3) (請先閲請背而之注意事項#填寫本頁) 裝. 實施例1 5和比較實施例D 增強網條之N R化合物 線_ 一種鋼筷之除渣粗钼料(見表1 0 )以B C I - E S 2依照實施Μ之程序化合,:,在1 5 0及1 7 0 C下壓縮模 化至最適熟化並於1 7 0 t過度熟化3 0分鐘以碕化該化 台·物,: 經沭部中央標準局CS:工消赀合作杜印¾.2 4 hours 7 2 hours c 14 c 1 4 (without SCI) (BCI-ES 2) (without BCI) (BCI-ES (please read the precautions first and then the tips page) install · hit _ line · The Ministry of Economic Affairs, Central Bureau of Precision Engineering, Migong Consumers Cooperated with Duyin ¾. 65 (67) (73) Tension (MPa) 25.3 25.5 2 0.2 20.1 (15.6) (21.1) (12.9) (17.1) This paper scale uses China a Standard (CNS) 1? *! Specifications (210x297 public) 2 〇9 Λ 6 li 6 V. Description of invention () Modulus 502 (MPa) 1.7 1.7 (1.2) (1.6) 1.4) 1.9 (1.9) Modulus lOOUHPa) 3.4 3.3 (1.9) (2.9) 2.3) (3.5) Modulus 3 0 0 UMPa) 15.8 15.5 (9.0) (14.2) 15.5 16.2 (9.8) (15.3) (Please read the notes on the back # fill in This page) is installed. Example 15 and Comparative Example D NR compound thread of reinforced wire mesh _ A slag-removing crude molybdenum material for steel chopsticks (see Table 10) is combined with BCI-ES 2 according to the procedure of implementing Μ: , Compression molding at 1 50 and 1 70 C to the most suitable aging and over-aging at 1 70 t for 30 minutes to stagnate the material, through the CS of the Ministry of Standardization of the Ministry of Labor: Cooperation Du Yin ¾.
r · ·- w NR 3HR CV 100.00 100.00 瑱黒N - 3 2 6 5 5.00 5 5.00 硬脂酸 0.50 0.50 氣化鋅 S . 0 0 8.00 芳族油 D u t r e X 7 2 9 Η P 3.00 3.00 Q 本紙法尺度边用中S H家標準(CNS) 規格(210X297公龙) 五、發明説明() Λ 6 Η 6r ·-w NR 3HR CV 100.00 100.00 YN-3 2 6 5 5.00 5 5.00 Stearic acid 0.50 0.50 Vaporized zinc S. 0 0 8.00 Aromatic oil D utre X 7 2 9 Η P 3.00 3.00 Q Original paper method Standard Chinese Standards (CNS) Standard (210X297 Male Dragon) for Standard Use V. Description of Invention () Λ 6 Η 6
Pernanex 6PPD 2.00 2.00 BCI-ES2 1.00 - Parkscit CBS 0.70 0.70 Crystex 0T 20 5.00 5.00 除上述之方法外, 並採用以下之試驗方法。 經濟部中央標準局β工消费合作社印奴 鋼筷之磨蝕:ASTM D-2295 蒸汽熟化 :3小時於1 1 9 °C及1 b a r壓力下 表1 1顎示B C Ϊ - E S 2對過早硫化並無影W巨可增加 <3力矩。 表1 1 溫度:1 5 0 3C Μ ο n a s n t 〇流度計熟化數據 過早硫化M S 1 2 1 Γ «—s / t,. \ t S 匕 I 7T ! (5力矩 ΐ N m ) 溫度:1 7 0 °C Μ ο n a s n t ο流度計熟化數據 t s 2 (分) 3力矩(N m ) _ ο Ο _ D 對照 D 對照 (請先閲請背而之注意事項再塡寫本頁) 5Pernanex 6PPD 2.00 2.00 BCI-ES2 1.00-Parkscit CBS 0.70 0.70 Crystex 0T 20 5.00 5.00 In addition to the above methods, the following test methods are used. Abrasion of Inno Steel Chopsticks by β Industry Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs: ASTM D-2295 Steam Curing: 3 hours at 1 1 9 ° C and 1 bar pressure Table 1 below 1 jaw shows BC Ϊ-ES 2 premature vulcanization There is no shadow W giant can increase < 3 moment. Table 1 1 Temperature: 1 5 0 3C Μ ο nasnt 〇 Fluidometer aging data premature vulcanization MS 1 2 1 Γ «—s / t ,. \ t S dagger I 7T! (5 moment l N m) Temperature: 1 7 0 ° C Μ ο nasnt ο Flowmeter maturation data ts 2 (min) 3 torque (N m) _ ο Ο _ D control D control (please read the precautions before writing this page) 5
BCI -ES 5BCI -ES 5
B C· I - Ξ S 本紙5IL尺度边用中a困家標準規格(210x297公¢) Λ 6 Η 6 209.加 五、發明説明( 經濟部中央標準局ΚΧ工消费合作杜印驭 表12顯示BCI—ES2保留甚或改善了許多機械性質 如硬度,張力, 模數及 拉扯強度,特別 地是,該1 7 0 t 過度熟化後,Β C I - E S 2亦改善了銅條之磨蝕性質。 表1 2 最適熟化之溫度 1 5 0 f 17 0 1 測試 D 15 D 1 5 (無 BCI) (BCI-ES2) (無 BCI) (BCI-ES2) 硬度(IRHD) δ δ 7 1 64 63 張力 (MPa) 2 5.3 2 5.4 2 5.5 25.9 模數 5 G % ( Μ P a ) 1.5 2.3 1 . 5 1.7 模數 1 G 0 :U Η P a ) 2.7 3.8 2.7 Λ <*» J “ 模數 3 0 0 S ( Μ P a ) 12. 4 15.5 11.6 13.6 拉扯強度(K N / a ) 114 98 10 7 1 0 2 網饶之磨蝕u) 2 9 0 3 5 0 130 19 0 熟化3 0分fl 1 7 0 t 澍試 D (無 E C I ) 1 HSU 丄- 硬度(I R H D ) 5 5 6 5 張力 (HP a) 19.0 2 2.2 模數 5 0 S (ϋ P a) 1 . 2 1.8 模數 100% (MPa) 1.8 3.1 模數 30〇UHPa) 7.9 13.6 9 1- 本紙张尺度边用中a Η家楳準(CNS) Ή規怙(210x297公及) (請先閲讀背而之注意事項再填窍本頁) 订· 線· 209班 Λ 6 Π 6 五、發明説明() 拉扯強度 (KN/di) 35 50 鋼條之磨 蝕(N) 4 10 44 0 實施例1 6 ,比較實施例E (雙馬來醯亞胺化合物)及比 較實施例F (無輔肋割之對照)。含B C I _ P h 2 (與 雙(4 _馬來醯亞胺苯基)二硫化物(B C I - P h 2 ) 和對照組(實施例F )比較)之N R化合物。 混合以N R為主之化合物(N R S H R C V 5 1 0 0份,碩黑 N - 3 3 0 5 0 P h r ,硬脂謗 2 P h r Ζ η 0 5 P h r , P e r k a c i t Μ B T S K 0 Phr,硫 2.25Phr)與 3.3 ?hr BCI-Ph2和 3.0Phr BMI-Ph2 ( 每1 〇 Q克物質7 . 5毫莫耳!。含B C I - P h 2之化合物不顯示 返原現象且在5 0 分Μ , 5.U 3 0 f熟化後較對照化合物和含 Β Η I - P h 2 之化合符具較高之殘留力矩,上逑後者兩化合物 均頴示具有明頚均的涅原現戈ί表1 3 ): 表 3 留力矩ί % (請先閲請背而之注意事項#塡寫本頁) 裝. 線- 經濟部中央標準局A工消伢合作杜印製 C I 一 p h 2 12 B Γ T -P 2 7 含B C I — P h 2之化合物在1 8 0 f硫化至最適熟 化及過屋熟化丨3 0分篷)後對對照化合物頭示了改 k紙張尺度逍用中a Η家標準(CNS) T4規格(210x297公放) 2〇9 ^ 上 五、發明説明() 善之機械性質,特別是在過度熟化後(表14):BC · I-Ξ S paper 5IL standard edge-use medium standard standard (210x297 cm) Λ 6 Η 6 209. Plus five, description of invention (Ministry of Economic Affairs Central Standards Bureau ΚΧIndustry and consumer cooperation Du Yinyu table 12 shows BCI —ES2 retains or even improves many mechanical properties such as hardness, tension, modulus and tensile strength, especially after the 1 70 t over-cure, Β CI-ES 2 also improves the abrasive properties of copper bars. Table 1 2 Optimum curing temperature 1 5 0 f 17 0 1 Test D 15 D 1 5 (without BCI) (BCI-ES2) (without BCI) (BCI-ES2) Hardness (IRHD) δ δ 7 1 64 63 Tension (MPa) 2 5.3 2 5.4 2 5.5 25.9 Modulus 5 G% (Μ P a) 1.5 2.3 1.5. 1.7 Modulus 1 G 0: U Η P a) 2.7 3.8 2.7 Λ < * »J" Modulus 3 0 0 S ( Μ P a) 12. 4 15.5 11.6 13.6 Tensile strength (KN / a) 114 98 10 7 1 0 2 Abrasion of net rao u) 2 9 0 3 5 0 130 19 0 Maturation 3 0 points fl 1 7 0 t test D (without ECI) 1 HSU-Hardness (IRHD) 5 5 6 5 Tension (HP a) 19.0 2 2.2 Modulus 5 0 S (ϋ P a) 1.2 1.8 Modulus 100% (MPa) 1.8 3.1 Modulus 30〇UHPa) 7.9 13.6 9 1- This paper is used in the marginal standard a 漢 家 楳 准 (CNS) Ή regulations (210x297) (Please read the precautions before filling in this page) Order · Line · 209 Class Λ 6 Π 6 5. Description of the invention () Tensile strength (KN / di) 35 50 Abrasion of steel bars (N) 4 10 44 0 Example 16 6, Comparative Example E (bismaleimide compound) and Comparative Example F (Control without auxiliary rib cutting). Contains BCI _ P h 2 (compared with bis (4 _ maleimide phenyl) disulfide (BCI-P h 2) and the control group (Example F)) NR compound. Mix NR-based compound (NRSHRCV 5 1 0 0 parts, Shuo black N-3 3 0 5 0 P hr, stearin 2 P hr AZ η 0 5 P hr, P erkacit Μ BTSK 0 Phr, Sulphur 2.25Phr) and 3.3 hr BCI-Ph2 and 3.0Phr BMI-Ph2 (7.5 millimoles per 10 gram substance! . Compounds containing BCI-P h 2 do not show reversion and have a higher residual moment after curing at 50 min M, 5.U 3 0 f than the control compound and the compound containing B Η I-P h 2, Both the latter two compounds are shown in the table below. The table 1 3): Table 3 Retention torque% (please read the back to the note # 塡 写 此 页) Pack. Thread-Economy Ministry of Central Bureau of Standards A, industrial and consumer cooperation cooperated to produce CI 1 ph 2 12 B Γ T -P 2 7 compounds containing BCI — P h 2 were cured at 1 800 f to optimal maturation and over-mature maturity 丨 30 0 tent ) The control compound was shown in the paper standard for the use of a standard (CNS) T4 specification (210x297 public release) 2〇9 ^ The fifth, invention description () good mechanical properties, especially after over-aging (Table 14):
表1 4 化合物 對照組 BCI -Ph2 熟化時間 t 9 0 6 0分鐘 t 90 6 0分鐘 硬度(S h A ) 15 2 3 17 23 張力(MPa) 18.6 13.4 2 1.6 1 7 . C 模數(HPa) 10 0¾ 1.5 1.5 2.0 4 . 3 3 0 0 ¾ 7.2 S . 2 9.4 1 6 . Q (請先閲讀背而之注意事項洱填寫本頁) 裝· 訂- 線 經消部中央櫺準局β工消伢合作杜印5i 本紙尺度逍用中SB家楳準(CNS)TM規怙(210x297公;!ί)Table 14 Compound control group BCI-Ph2 curing time t 9 0 6 0 minutes t 90 6 0 minutes Hardness (S h A) 15 2 3 17 23 Tension (MPa) 18.6 13.4 2 1.6 1 7. C modulus (HPa) 10 0¾ 1.5 1.5 2.0 4. 3 3 0 0 ¾ 7.2 S. 2 9.4 1 6. Q (please read the precautions first and fill in this page) Binding · Ordering-Central Economic Development Bureau of the Ministry of Economics and Trade Cooperate with Duyin 5i on this paper, and use it in SB Family Standard (CNS) TM regulations (210x297;! Ί)
Claims (1)
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EP (2) | EP0555288B1 (en) |
JP (2) | JPH06502150A (en) |
KR (2) | KR100192077B1 (en) |
CN (2) | CN1042734C (en) |
AR (1) | AR247412A1 (en) |
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CA (2) | CA2095135A1 (en) |
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ES (2) | ES2088505T3 (en) |
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PL (2) | PL169601B1 (en) |
RU (2) | RU2067974C1 (en) |
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TW (1) | TW209231B (en) |
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1995
- 1995-03-30 US US08/413,567 patent/US5610240A/en not_active Expired - Lifetime
- 1995-11-29 GR GR950403332T patent/GR3018216T3/en unknown
-
1996
- 1996-06-27 GR GR960401754T patent/GR3020382T3/en unknown
Also Published As
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